CNT-BASED SENSORS: DEVICES, PROCESSES AND USES THEREOF

• US 20110163296A1
• Filed: 01/26/2007
• Published: 07/07/2011
• Est. Priority Date: 01/26/2006
• Status: Active Grant

• Current Assignee: Nanoselect, Inc.
• Original Assignee: Nanoselect, Inc.
• Inventors: Patil, Ajeeta Pradip, Tan, Kah Fatt, Man, Piu Francis, Pace, Salvatore J.
• Granted Patent: US 8,907,384 B2
• Time in Patent Office: Days
• US Class Current: 257/24
• 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; and

an assembly of doped antennae vertically oriented with respect to the electrically conductive layer, 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 at least a portion of the outer surface of the mid-section is capable of being in fluidic contact with an environment in contact with the antennae;

a top end disposed opposite to the base end, 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 PTFE, 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(NH₃)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 52, wherein the metal comprises a CVD-deposited metal.

54. The antennae assembly electrode of claim 52, 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.

69a. a. 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.

69b. b. 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

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.

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

190. A sensor comprising the antennae assembly electrode according to claim 1.

191. A field-effect transistor comprising the antennae assembly electrode according to claim 1.

208. The antennae assembly electrode of claim 3, wherein the metals comprise a metal atom, a metal oxide, a metal halide, a metal alloy, or any combination thereof.

209. The antennae assembly electrode of claim 3, wherein the metal comprises Ag, Au, Zn, Cu, or any combination thereof.

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

211. The antennae assembly of claim 210, wherein tether comprises an alkane, an olefin, a linear hydrocarbon, a branched hydrocarbon, or any combination thereof.

78. A method of making an antennae assembly electrode, comprising the steps of:

surmounting a substrate with an electrically conductive layer;

surmounting an assembly of antennae on the electrically conductive layer giving rise to the antennae being vertically oriented with respect to the electrically conductive layer, wherein each of the antennae comprises a MWNT comprising a base end being attached to the electrically conductive layer;

a mid-section comprising an outer surface surrounding a lumen, wherein at least a portion of the outer surface of the mid-section is capable of being in fluidic contact with an environment in contact with the antennae; and

a top end being disposed opposite to the base end; and

doping at least a portion of the MWNT with a cladding, a covalent bond linkage, a functional dopant molecule, a fill material, or any combination thereof.

79. The method of claim 78, further comprising the step of surmounting the substrate with a thermal oxide layer, wherein the electrically conductive layer surmounts the thermal oxide layer.

80. The method of claim 79, further comprising the step of surmounting the thermal oxide layer with an electrically conductive contact pad.

81. The method of claim 78, wherein the electrically conductive layer is surmounted to the substrate using a chemical vapor deposition process, a sputtering process, a fluid deposition process, or any combination thereof.

82. The method of claim 78, wherein a catalyst is surmounted to the electrically conductive layer using a chemical vapor deposition process, a sputtering process, a fluid deposition process, or any combination thereof.

83. The method of claim 82, wherein the chemical vapor deposition process includes a gas phase thermal chemical vapor deposition method, a solid precursor chemical vapor deposition method, a plasma-enhanced chemical vapor deposition method, or any combination thereof.

84. The method of claim 82, wherein the chemical vapor deposition method includes microwave stimulation, radio frequency plasma stimulation, direct current plasma field enhancement, laser energy enhancement or any combination thereof.

85. The method of claim 78, wherein the step of surmounting an assembly of antennae includes end-linking a plurality of MWNT to the conductive layer.

86. The method of claim 85, wherein the plurality of MWNT self-assemble on the conductive layer.

87. The method of claim 85, wherein the MWNT comprise an end-functionalized MWNT.

88. The method of claim 85, wherein the conductive layer comprises functional groups that link to the ends of the MWNT.

89. The method of claim 88, wherein the MWNT comprise an end-functionalized MWNT.

90. The method of claim 85, wherein the MWNT are provided as a dispersion of a plurality of MWNT in a fluid.

91. The method of claim 90, wherein the fluid is an organic liquid, an aqueous liquid, or any combination thereof.

92. The method of claim 78, wherein the step of surmounting an assembly of antennae includes growing an assembly of MWNT on the conductive layer.

93. The method of claim 92, wherein the step of growing an assembly of MWNT includes gas phase thermal vapor deposition, solid precursor chemical vapor deposition, plasma enhanced chemical vapor deposition, laser enhanced CVD or any combination thereof.

94. The method of claim 78, wherein the step of surmounting an assembly of antennae includes surmounting the conductive layer with catalyst and contacting a MWNT forming composition and the catalyst at conditions necessary to grow the assembly of MWNT from the catalyst.

95. The method of claim 94, wherein the step of growing an assembly of MWNT includes gas phase thermal vapor deposition, solid precursor chemical vapor deposition, plasma enhanced chemical vapor deposition, or any combination thereof.

96. The method of claim 94, wherein the MWNT forming composition comprises, an organometallic precursor, or any combination thereof.

97. The method of claim 96, wherein the organometallic precursor comprises a phthalocyanine, a porphorin, a carbon bearing ligand, or any combination thereof.

98. The method of claim 97, wherein the organometallic precursor comprises iron(II) phthalocyanine.

99. The method of claim 97, wherein the carbon bearing ligand comprises a transition metal chelate including Fe, Co, Ni, Ru, Os, Eu, or any combination thereof.

100. The method of claim 94, wherein the MWNT forming composition comprises one or more molecules composed of covalently bonded carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, or any combination thereof.

101. The method of claim 100, wherein the molecules include gases comprising methane, ethane, propane, butane, ammonia, acetylene, ethylene, propylene, or any combination thereof.

102. The method of claim 100, wherein the molecules include liquids comprising aliphatic hydrocarbons, olefins, or any isomer or combination thereof.

103. The method of claim 94, wherein the conditions necessary to form the assembly of MWNT includes a temperature in the range of from about 300°

C. to about 1000°

C. and a pressure in the range of from about 10<sup>−

1</sup> ton to 10<sup>−

9</sup> ton.

104. The method of claim 103, wherein the conditions necessary to form the assembly of MWNT includes a temperature in the range of from about 500°

C. to about 700°

C. and a pressure in the range of from about 10<sup>−

6</sup> ton to 10<sup>−

9</sup> ton.

105. The method of claim 103, wherein plasma-enhanced chemical vapor deposition is used to form the MWNT.

106. The method of claim 78, wherein the step of doping includes liquid coating, chemical vapor deposition, ion beam deposition, electrospray coating, supercritical fluid solute phase transfer, or any combination thereof.

107. The method of claim 106, wherein the ion beam deposition includes electro-spray ionization, electron beam deposition, proton beam deposition, atomic ion beam deposition, molecular beam deposition, or any combination thereof.

108. The method of claim 78, further comprising the step of depositing a metal on the electrically conductive layer to provide an electrode contact pad.

109. The method of claim 108, wherein the electrode contact pad is distally located from the assembly of MWNT.

110. The method of claim 78, further comprising the step of patterning the assembly of MWNT.

111. The method of claim 110, wherein the step of patterning gives rise to an array of MWNT.

112. The method of claim 110, wherein the step of patterning includes photolithography, UV lithography, e-beam lithography, reactive ion etching, chemical etching, nano-imprinting, electro-forming, or any combination thereof.

113. The method of claim 78, further comprising the step of patterning the electrically conductive layer.

114. The method of claim 113, wherein the step of patterning gives rise to an array of MWNT.

115. The method of claim 113, wherein the step of patterning includes photolithography, UV lithography, e-beam lithography, reactive ion etching, chemical etching, nano-imprinting, electro-forming, electrochemical polymerization, or any combination thereof.

116. The method of claim 78, wherein the step of surmounting the substrate with an electrically conductive layer includes electroforming, electro-less deposition, electrochemical deposition, vapor deposition, sputtering, or any combination thereof.

117. The method of claim 78, wherein the assembly of doped MWNT comprise a plurality of MWNT having a fill material.

118. The method of claim 117, wherein the fill material includes molecules, molecular ions, atoms, atomic ions, or any combination thereof.

119. The method of claim 117, wherein the fill material includes one or more fullerenes, doped fullerenes, ionophores, ion exchangers, redox molecules, conductive polymers, or any combination thereof.

120. The method of claim 119, wherein the ionophores include cyclic polyethers, antibiotics, linear chain ligands or any combination thereof.

121. The method of claim 120, wherein the cyclic polyethers comprise 12-crown-4 to 24-crown-8 polyethers, or any combination thereof.

122. The method of claim 120, wherein the ionophores includes one or more cryptands, calixarenes, rotaxanes, or any combination thereof.

123. The method of claim 119, wherein the fullerenes include one or more of C₆₀, C₇₀, C₈₀, C₉₀, or any combination thereof.

124. The method of claim 119, wherein the fullerenes are doped fullerenes.

125. The method of claim 124, wherein the doped fullerenes are filled, coated, chemically functionalized, or any combination thereof.

126. The method of claim 119, wherein the ion exchangers include quaternized PVC, sulfonated TPFE, or any combination thereof.

127. The method of claim 120, wherein the antibiotics include valinomycin, nonactin, monensin, iosin, or any combination thereof.

128. The method of claim 120, 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, tridodecylamine, or any combination thereof.

129. The method of claim 117, wherein the fill material includes semiconductor polymers comprising donor-acceptor pairs.

130. The method of claim 129, wherein the semiconductor polymers comprise donor-acceptor pairs include semicarbazole/TCNQ, ionene/iodine, or any combination thereof.

131. The method of claim 117, wherein the fill material includes conductive polymers.

132. The method of claim 131, wherein the conductive polymers comprise a polypyrrole, a polyaniline, a poly-p-phenylene, a polyacetylene, a polythiophene, or any combination thereof.

133. The method of claim 117, wherein at least two of the doped MWNT comprise different fill molecules.

134. The method of claim 117, wherein the fill material includes a chemical agent capable of responding to a chemical or an electrical signal.

135. The method of claim 78, wherein at least a portion of the MWNT are doped with a cladding.

136. The method of claim 135, 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.

137. The method of claim 136, wherein the dielectric includes a polyolefin polymer, a polyaliphatic polymer, a polysiloxane polymer, a polyurethane polymer, a polyvinylchloride polymer, alumina, or any combination thereof.

138. The method of claim 136, wherein the ion conducting polymer includes nafion, polystyrene sulfonate, polyvinylpridinium, or any combination thereof.

139. The method of claim 136, wherein the electron conducting polymer includes a doped polymer, an electrochemically doped polymer, a redox electroactive polymer, or any combination thereof.

140. The method of claim 139, wherein the doped polymer includes a polyionine, a polysilicon, a polysemicarbazole, a polyphenylene, a polyacetylene, a polyphenylene sulfide, or any combination thereof.

141. The method of claim 140, wherein the doped polymer includes a dopant, the dopant comprising AsF₅, I₂, Li, K, BF₆-, PF₆-, or any combination thereof.

142. The method of claim 139, wherein the electrochemically doped polymer includes a polypyrrole, a polythiophene, a polyphenylquinone, a polyaniline, or any combination thereof.

143. The method of claim 139, wherein the redox electroactive polymers include polyviologen, polyvinylferrocene, poly-Ru(vbpy)3++, or any combination thereof.

144. The method of claim 136, 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.

145. The method of claim 136, wherein the redox-mediator dopant includes Ru(bpy)3++, Br2/Br−

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

), Ru(NH3)6+++, quinone, hydroquinone, methylviologen, tetracyanoquinodimethane, benzophenone, ferrocene, tetramethyl-p-phenylenediamine, tetrathiafulvalene, tri-N-p-tolylamine, or any combination thereof.

146. The method of claim 135, wherein the cladding comprises one or more functional reactive groups residing upon a surface of the cladding.

147. The method of claim 146, 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.

148. The method of claim 135, wherein the cladding includes a covalent bond linkage attaching the cladding to the doped MWNT.

149. The method of claim 148, wherein the covalent bond linkage includes a Schiff base, a carbodi-imide, an amide, or any combination thereof.

150. The method of claim 135, wherein the cladding is linked to a selective functionality on the surface of one or more of the MWNT.

151. The method of claim 150, wherein the selective functionality on the surface of one or more of the MWNT includes a protein, a phospholipids, a nucleic acid, an electron mediator, an ionophore, or any combination thereof.

152. The method of claim 151, wherein the protein includes an enzyme, an antibody, an antigen or any combination thereof.

153. The method of claim 151, wherein the nucleic acid includes an oligonucleotide, DNA, RNA, or any combination thereof.

154. The method of claim 135, wherein at least two of the doped MWNT comprise different claddings.

156. The method of claim 78, wherein at least a portion of the MWNT are doped with a functional dopant molecule.

157. The method of claim 156, wherein the MWNT comprise one or more functional dopant molecules covalently attached to the graphene surface of the MWNT.

158. The method of claim 157, wherein the functional dopant molecules 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.

159. The method of claim 78, wherein at least a portion of the MWNT are doped with a covalent bond linkage that is covalently linked to the graphene surface of the MWNT.

160. The method of claim 159, wherein the covalent bond linkage includes a Schiff base, a carbodi-imide, an amide, or any combination thereof.

161. The method of claim 156, wherein the functional dopant molecules covalently attached to the graphene surface using a selective functionality.

162. The method of claim 161, wherein the selective functionality includes a protein, a phospholipids, a nucleic acid, an electron mediator, an ionophore, or any combination thereof.

163. The method of claim 162, wherein the protein includes an enzyme, an antibody, or any combination thereof.

164. The method of claim 162, wherein the nucleic acid includes an oligonucleotide, DNA, RNA, or any combination thereof.

165. The method of claim 78, wherein the electrically conductive layer comprises a metal, an electrically conductive polymer, a carbon film, or any combination thereof.

166. The method of claim 165, wherein the electrically conductive layer is capable of being a lead conductor residing between the substrate and a catalyst surmounted to the electrically conductive layer.

167. The method of claim 78, wherein the electrically conductive layer comprises Pt, Au, Ti, W, V, Mo, or any combination thereof.

168. The method of claim 167, wherein the metal comprises a CVD-deposited metal.

169. The method of claim 167, wherein the CVD-deposited metal comprises TiW, Mo, TiN, or any combination thereof.

170. The method of claim 78, wherein the electrically conductive layer is characterized as having a layer thickness in the range of from about 1 nanometer to about 1000 nanometers.

171. The method of claim 78, wherein the electrically conductive layer is characterized as having a layer thickness in the range of from about 10 nanometers to about 100 nanometers.

172. The method of claim 78, wherein the electrically conductive layer is characterized as having a layer thickness in the range of from about 50 nanometers to about 100 nanometers.

173. The method of claim 78, wherein the catalyst comprises Fe, Co, Ni, Mo, Ru, Pt, Cr, Pd, Si, Tb, Se, Cu, Al, Rh, Os, Ir, or any combination or alloy thereof.

174. The method of claim 173, wherein the catalyst comprises Pd powder, Ni silicide, Fe—

Ni alloy, Fe—

Ni—

Cr alloy, Mo—

Fe alloy film, Fe—

Tb alloy, Pd—

Se alloy, Cu—

Ni alloy, Co—

Cu alloy, Al—

Fe alloy, Cu—

Fe alloy, Fe—

Ni alloy, Alumina-Ni alloy, Alumina-Ni—

Cu alloy, or any combination thereof.

175. The method of claim 173, wherein the catalyst comprises an organo-metallic catalyst, an iron-phthalocyanine, a cobalt-phthalocyanine, or any combination thereof.

176. The method of claim 173, wherein the catalyst comprises a catalysts capable of growing MWNT.

177. The method of claim 176, wherein the catalysts capable of growing MWNT includes nickel, cobalt, iron, or any combination thereof.

178. The method of claim 82, wherein the catalyst is characterized as having a layer thickness in the range of from about 1 nanometer to about 10,000 nanometers.

179. The method of claim 178, wherein the catalyst is characterized as having a layer thickness in the range of from about 500 nanometers to about 1000 nanometers.

180. The method of claim 179, wherein the catalyst is characterized as having a layer thickness in the range of from about 700 nanometers to about 900 nanometers.

181. The method of claim 78, wherein the doped antennae assembly comprises a plurality of doped MWNT perpendicularly oriented to the substrate.

182. The method of claim 181, wherein the doped MWNT are oriented parallel to each other.

183. The method of claim 78, wherein the assembly of doped MWNT comprises a doped MWNT carpet, a doped MWNT array, or any combination thereof.

184. The method of claim 183, 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.

185. The method of claim 183, 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.

186. The method of claim 78, wherein the assembly of doped MWNT comprises an array of doped MWNT.

187. The method of claim 82, wherein the catalyst is patterned on the electrically conductive layer, and the assembly of doped MWNT is attached to the patterned catalyst.

188. The method of claim 82, wherein the catalyst is patterned as an array of islands, stripes, circles, squares, rings, triangles, polygons, or any combination thereof.

189. An antennae assembly electrode made according to the method of claim 78.

192. An antennae assembly field-effect transistor, comprising:

a substrate comprising a source and a drain;

a gate oxide layer at least partially surmounting the substrate, source and drain;

an electrically conductive layer at least partially surmounting the gate oxide layer; and

an assembly of doped MWNT antennae vertically oriented with respect to the electrically conductive layer.

193. A sensor, comprising:

at least two electrodes situated on a substrate, wherein at least one of the electrodes comprises

an antennae assembly electrode, wherein the antennae assembly electrode comprises

an electrically conductive layer at least partially surmounting a substrate; and

an assembly of doped antennae vertically oriented with respect to the electrically conductive layer, 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 at least a portion of the outer surface of the mid-section is capable of being in fluidic contact with an environment in contact with the antennae;

a top end disposed opposite to the base end, 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 with the top end, or any combination thereof.

194. The sensor of claim 193, wherein the electrodes include at least one working electrode, at least one reference electrode, or both.

195. The sensor of claim 194, wherein at least one working electrode comprises a antennae assembly electrode.

196. The sensor of claim 194, wherein at least one reference electrode comprises a antennae assembly electrode.

197. The sensor of claim 194, wherein at least one working electrode and at least one reference electrode comprises a antennae assembly electrode.

198. The sensor of claim 194, wherein the reference electrode is situated on a field-effect transistor.

199. The sensor of claim 198, wherein the field-effect transistor comprises a source and a drain, the source and drain being electrically connected by conductive leads to electrical contacts situated on the substrate.

200. The sensor of claim 199, wherein the filed-effect transistor comprises:

a gate oxide layer at least partially surmounting the substrate, source and drain;

the electrically conductive layer at least partially surmounting the gate oxide layer; and

the assembly of doped MWNT vertically oriented with respect to the electrically conductive layer.

201. The sensor of claim 193, further comprising a counter electrode.

202. The sensor of claim 201, wherein the counter electrode comprises a antennae assembly electrode, a metallic electrode, or any combination thereof.

203. The sensor of claim 202, wherein the metallic electrode is composed of gold, silver, platinum, palladium, copper, iron, titanium, tungsten, or any combination thereof.

204. The sensor of claim 201, further comprising electrically conducting leads connecting each of the electrodes to an electrical contact situated on the substrate.

205. An antennae assembly electrode, comprising:

an electrically conductive layer at least partially surmounting a substrate; and

an assembly of antennae vertically oriented with respect to the electrically conductive layer, 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 at least a portion of the outer surface of the mid-section is capable of being in fluidic contact with an environment in contact with the antennae; and

a top end disposed opposite to the base end.

206. A sensor comprising the antennae assembly electrode according to claim 205.

207. A field-effect transistor comprising the antennae assembly electrode according to claim 205.

212. A method of making an antennae assembly electrode, comprising the steps of:

surmounting a substrate with an electrically conductive layer; and

surmounting an assembly of antennae on the electrically conductive layer giving rise to the antennae being vertically oriented with respect to the electrically conductive layer, wherein each of the antennae comprises a MWNT comprising a base end being attached to the electrically conductive layer;

a mid-section comprising an outer surface surrounding a lumen; and

a top end being disposed opposite to the base end.

213. The method according to claim 212, further comprising doping at least a portion of the MWNT with a cladding, a covalent bond linkage, a functional dopant molecule, a fill material, or any combination thereof.

214. The method according to claim 212, further comprising:

conformally depositing an insulating material on each of the antennae and the electrically conductive layer;

depositing a photoresist layer on the insulating material;

imaging at least a portion of the photoresist to give rise to an imaged photoresist portion and an unimaged photoresist portion;

removing a portion of the imaged photoresist portion or the unimaged photoresist portion to expose the insulating material conformally deposited on the top end of the MWNT and a portion of the mid-section of the MWNT; and

removing the insulating material conformally deposited on the top end of the MWNT and a portion of the mid-section of the MWNT to give rise to an exposed top portion of the MWNT.

215. The method of claim 212, further comprising contacting the exposed top portion of the MWNT with a super critical solution comprising a super critical solvent and a dopant.

216. A method of growing non-aligned MWNTs on a substrate, comprising:

depositing a nickel metal catalyst on a substrate; and

contacting the nickel metal catalyst with a gas mixture comprising a carrier gas and a carbon source gas at a temperature in the range of from about 650°

C. to about 750°

C., the carbon source gas comprising acetylene, wherein the substrate comprises silicon, silicon dioxide, silicon nitride, phosphorus doped poly silicon, or boron doped P-type silicon, to give rise to non-aligned MWNTs attached to the nickel metal catalyst.

217. A method of growing aligned MWNTs on a substrate, comprising:

contacting a substrate with a gas comprising a carrier gas and a carbon source gas at a temperature in the range of from about 800°

C. to about 960°

C., the carbon source gas comprising iron (II) phthalocyanine, wherein the substrate comprises silicon, silicon dioxide, silicon nitride, phosphorus doped poly silicon, or boron doped P-type silicon, to give rise to aligned MWNTs attached to the substrate.

218. The method of claim 217, wherein at least a portion of the substrate comprises a copper pattern, whereby essentially no MWNTs grow on the copper pattern.

219. A method of growing aligned MWNTs on a substrate, comprising:

depositing a nickel metal catalyst on the titanium barrier layer; and

contacting the nickel metal catalyst with a gas mixture comprising a carrier gas and a carbon source gas at a temperature in the range of from about 650°

C. to about 750°

C., the carrier gas comprising argon, ammonia and hydrogen, the carbon source gas comprising acetylene, wherein the substrate comprises silicon, silicon dioxide, silicon nitride, phosphorus doped poly silicon, or boron doped P-type silicon, to give rise to aligned MWNTs attached to the nickel metal catalyst.