Method for forming an array of single-wall carbon nanotubes and compositions thereof

• US 20020159943A1
• Filed: 12/28/2001
• Published: 10/31/2002
• Est. Priority Date: 03/07/1997
• Status: Active Grant

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Smalley, Richard E., Liu, Jie, Rinzler, Andrew G., Nikolaev, Pavel, Colbert, Daniel T., Thess, Andreas, Hafner, Jason H., Smith, Ken, Guo, Ting, Dai, Hongjie
• Granted Patent: US 7,205,069 B2
• Time in Patent Office: Days
• US Class Current: 423/447.1
• CPC Class Codes: B01J 19/081 employing particle radiation or gamma-radiation
• CPC Class Codes: B01J 19/087 employing electric or magnetic energy
• CPC Class Codes: B01J 19/10 employing sonic or ultrasonic vibrations
• CPC Class Codes: B01J 19/121 Coherent waves, e.g. laser beams lasers per se H01S3/00
• CPC Class Codes: B01J 19/126 Microwaves
• CPC Class Codes: B01J 19/129 Radiofrequency
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 2219/00078 Fingers
• CPC Class Codes: B01J 2219/0892 involving catalytically active material
• CPC Class Codes: B01J 23/74 Iron group metals
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/8913 Cobalt and noble metals
• CPC Class Codes: B01J 37/0238 via the gaseous phase-sublimation
• CPC Class Codes: B01J 37/349 making use of flames, plasmas or lasers
• CPC Class Codes: B82B 3/00 Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 32/156 After-treatment
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/17 Purification
• CPC Class Codes: D01F 9/12 Carbon filaments; Apparatus specially adapted for the manufacture thereof
• CPC Class Codes: D01F 9/127 : by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
• CPC Class Codes: D21H 27/00 : Special paper not otherwise provided for, e.g. made by multi-step processes
• CPC Class Codes: G11B 9/1418 : Disposition or mounting of heads or record carriers G11B17/00 and G11B19/00 take precedence
• CPC Class Codes: G11B 9/1445 : switching at least one head in operating function; Controlling the relative spacing to keep the head operative, e.g. for allowing a tunnel current flow
• CPC Class Codes: G11B 9/1472 : characterised by the form
• CPC Class Codes: G11B 9/149 : characterised by the memorising material or structure
• CPC Class Codes: G11C 13/0014 : comprising cells based on organic memory material
• CPC Class Codes: G11C 13/0019 : comprising bio-molecules
• CPC Class Codes: G11C 13/025 : using fullerenes, e.g. C60, or nanotubes, e.g. carbon or silicon nanotubes
• CPC Class Codes: G11C 2213/16 : Memory cell being a nanotube, e.g. suspended nanotube
• CPC Class Codes: G11C 2213/71 : Three dimensional array
• CPC Class Codes: G11C 2213/81 : Array wherein the array conductors, e.g. word lines, bit lines, are made of nanowires
• CPC Class Codes: H01G 9/2059 : comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• CPC Class Codes: H01L 31/0352 : characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
• CPC Class Codes: H01L 31/06 : characterised by potential barriers
• CPC Class Codes: H01L 31/18 : Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: H01M 10/0525 : Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/583 : Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: Y02E 10/542 : Dye sensitized solar cells
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 977/70 : Nanostructure
• CPC Class Codes: Y10S 977/742 : Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/745 : having a modified surface
• CPC Class Codes: Y10S 977/748 : Modified with atoms or molecules bonded to the surface
• CPC Class Codes: Y10S 977/75 : Single-walled
• CPC Class Codes: Y10S 977/753 : with polymeric or organic binder
• CPC Class Codes: Y10S 977/789 : in array format
• CPC Class Codes: Y10S 977/842 : for carbon nanotubes or fullerenes
• CPC Class Codes: Y10S 977/843 : Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/845 : Purification or separation of fullerenes or nanotubes
• CPC Class Codes: Y10S 977/847 : Surface modifications, e.g. functionalization, coating
• CPC Class Codes: Y10S 977/848 : Tube end modifications, e.g. capping, joining, splicing
• CPC Class Codes: Y10S 977/849 : with scanning probe
• CPC Class Codes: Y10S 977/882 : Assembling of separate components, e.g. by attaching
• CPC Class Codes: Y10S 977/948 : Energy storage/generating using nanostructure, e.g. fuel cell, battery
• CPC Class Codes: Y10T 428/24058 : including grain, strips, or filamentary elements in respective layers or components in angular relation
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]
• CPC Class Codes: Y10T 428/292 : In coating or impregnation
• CPC Class Codes: Y10T 428/30 : Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

A method for purifying a mixture comprising single-wall carbon nanotubes and amorphous carbon contaminate is disclosed The method includes the steps of heating the mixture under oxidizing conditions sufficient to remove the amorphous carbon, followed by recovering a product comprising at least about 80% by weight of single-wall carbon nanotubes. A method for producing tubular carbon molecules of about 5 to 500 nm in length is also disclosed. The method includes the steps of cutting single-wall nanotube containing-material to form a mixture of tubular carbon molecules having lengths in the range of 5-500 nm and isolating a fraction of the molecules having substantially equal lengths. The nanotubes may be used, singularly or in multiples, in power transmission cables, in solar cells, in batteries, as antennas, as molecular electronics, as probes and manipulators, and in composites.

Claims

1. A method for purifying a mixture comprising single-wall carbon nanotubes and amorphous carbon contaminate, said method comprising the steps of:

(a) heating said mixture under oxidizing conditions sufficient to remove the said amorphous carbon and

(b) recovering a product comprising at least about 80% by weight of single-wall carbon nanotubes.

2. The method of claim 1 wherein said oxidizing conditions comprise an aqueous solution of an inorganic oxidant.

3. The method of claim 2 wherein said inorganic oxidant is selected from the group consisting of nitric acid, a mixture of sulfuric acid and hydrogen peroxide, potassium permanganate and mixtures thereof.

4. The method of claim 2 wherein said aqueous solution is heated to reflux.

5. The method of claim 2 additionally comprising the step of subjecting the oxidized product of step (b) to a saponification treatment.

6. The method of claim 5 wherein said saponification treatment comprises contacting said product with a basic solution.

7. The method of a claim 6 wherein said basic solution comprises sodium hydroxide.

8. The method of claim 6 additionally comprising the step of neutralizing the saponified product with an acid.

9. The method of claim 8 wherein said acid is hydrochloric acid.

10. The method of claim 8 additionally comprising the step of recovering a solid product from the saponified, neutralized product.

11. The method of claim 10 wherein said product is recovered by a method selected from the group consisting of filtration, settling by gravity, chemical flocculators, and liquid cycloning.

12. The method of claim 10 wherein said solid product is a paper-like two dimensional product.

13. The method of claim 12 additionally comprising the step of drying the product.

14. The method of claim 13 wherein said product is dried at about 850°

C. in a hydrogen gas atmosphere.

15. The method of claim 1 wherein said product comprises at least about 90% by weight of single-wall carbon nanotubes.

16. The method of claim 1 wherein said product comprises at least about 95% by weight of single-wall carbon nanotubes.

17. The method of claim 1 wherein said product comprises at least about 99% by weight of single-wall carbon nanotubes.

19. The method of claim 18 wherein said cutting single-wall nanotubes into tubular carbon molecules comprising the steps of:

(a) forming a substantially two-dimensional target containing single-wall nanotubes of lengths up to about one micron or more, and

(b) irradiating said target with a high energy beam of high mass ions.

20. The method of claim 19 wherein a high energy beam is produced in a cyclotron and has an energy of from about 0.1 to about 10 GeV.

21. The method of claim 19 wherein said high mass ion has a mass of greater than about 150 AMU.

22. The method of claim 21 wherein said high mass ion is selected from the group consisting of gold, bismuth and uranium.

23. The method of claim of 22 wherein the high mass ion is Au⁺³³.

24. The method of claim 18 wherein said cutting single-wall nanotubes into tubular carbon molecules comprises the steps of:

(a) forming a suspension of single-wall nanotubes in a medium;

(b) sonicating said suspension with acoustic energy.

25. The method of claim 24 wherein said acoustic energy is produced by a device operating at 40 KHz and having an output of 20 W.

26. The method of claim 18 wherein said cutting single-wall nanotubes into tubular carbon molecules comprises refluxing single wall nanotube material in concentrated HNO₃.

27. The method of claim 19 further comprising the step of heating the tubular carbon molecules to form a hemispheric fullerene cap on at least one end thereof.

28. The method of claim 18 further comprising the step of reacting said tubular carbon molecules with a material which provides at the reaction conditions at least on substituent on at least one of said ends of said tubular carbon molecule.

29. The method of claim 26 further comprising the step of reacting said tubular carbon molecules with a material which provides at the reaction conditions at least one substituent on at least one of said ends of said tubular carbon molecule.

30. The method of claim 28 or 29 wherein said substituent is selected from the group consisting of each may be independently selected from the group consisting of hydrogen;

alkyl, acyl, aryl, aralkyl, halogen;

substituted or unsubstituted thiol;

unsubstituted or substituted amino;

hydroxy, and OR′

wherein R′

is selected from the group consisting of hydrogen, alkyl, acyl, aryl aralkyl, unsubstituted or sublet amino;

substituted or unsubstituted thiol; and

halogen; and

a linear or cyclic carbon chain optionally interrupted with one or more heteroatom, and optionally substituted with one or more ═

O, or ═

S, hydroxy, an aminoalkyl group, an amino acid, or a peptide of 2-8 amino acids.

18. A method for producing tubular carbon molecules of about 5 to 500 nm in length, said method comprising the steps of:

(a) cutting single-wall nanotube containing-material to form a mixture of tubular carbon molecules having lengths in the range of 5-500 nm;

(b) isolating from said mixture of tubular carbon molecules a fraction of said molecules having substantially equal lengths.

31. A method for forming a macroscopic molecular array of tubular carbon molecules, said method comprising the steps of:

(a) providing at least about 10⁶ tubular carbon molecules of substantially similar length in the range of 50 to 500 nm;

(b) introducing a linking moiety onto at least one end of said tubular carbon molecules;

(c) providing a substrate coated with a material to which said linking moiety will attach; and

(d) contacting said tubular carbon molecules containing a linking moiety with said substrate.

32. The method of claim 31 wherein said substrate is selected from the group consisting of gold, mercury and indium-tin-oxide.

33. The method of claim 32 wherein said linking moiety is selected from the group consisting of —

S—

, —

S—

(CH₂)_n—

NH—

, and —

SiO₃(CH₂)₃NH₃.

35. The method of claim 34 further comprising the step of applying an electric field in the vicinity of said substrate to assist in the alignment of said nanotubes growing from said microwells.

37. The method of claim 36 wherein said oxidizing conditions comprise heating said surface to about 500°

C. in an atmosphere of oxygen and CO₂.

39. The method of claim 38 wherein all the subarrays have the same type of nanotubes.

40. The method of claim 38 wherein the subarrays have different types of nanotubes.

41. The method of claim 38 wherein the subarrays are made according to the method of any of claims 31, 34 or 36.

34. A method for forming a macroscopic molecular array of tubular carbon molecules, said method comprising the steps of:

(a) providing a nanoscale array of microwells on a substrate;

(b) depositing a metal catalyst in each of said microwells; and

(c) directing a stream of hydrocarbon or CO feedstock gas at said substrate under conditions that effect growth of single-wall carbon nanotubes from each microwell.

36. A method for forming a macroscopic molecular array of tubular carbon molecules, said method comprising the steps of:

(a) providing surface containing purified but entangled and relatively endless single-wall carbon nanotube material;

(b) subjecting said surface to oxidizing conditions sufficient to cause short lengths of broken nanotubes to protrude up from said surface; and

(c) applying an electric field to said surface to cause said nanotubes protruding from said surface to align in an orientation generally perpendicular to said surface and coalesce into an array by van der Waals interaction forces.

38. A method of forming a macroscopic molecular array of tubular carbon molecules, said method comprising the step of assembling subarrays of up to 16 single-wall carbon nanotubes into a composite array.

42. A method for continuously growing macroscopic carbon fiber comprising at least about 10⁶ single-wall nanotubes in generally parallel orientation, said method comprising the steps of:

(a) providing a macroscopic molecular array of at least about 10⁶ tubular carbon molecules in generally parallel orientation and having substantially similar lengths in the range of from about 50 to about 500 nanometers;

(b) removing the hemispheric fullerene cap from the upper ends of the tubular carbon molecules in said array;

contacting said upper ends of the tubular carbon molecules in said array with at least one catalytic metal;

(d) supplying a gaseous source of carbon to the end of said array while applying localized energy to the end of said array to heat said end to a temperature in the range of about 500°

C. to about 1300°

C.; and

(e) continuously recovering the growing carbon fiber.

43. The method of claim 42 wherein said fullerene caps are removed by heating in an oxidative environment.

44. The method of claim 43 wherein said oxidative environment comprises aqueous etching with nitric acid or gas phase etching at temperatures of about 500°

C. in an atmosphere of oxygen, and CO₂.

45. The method of claim 42 wherein said catalytic metal is selected from the group consisting of Group VIII transition metals, Group VI transition metals, metals of the lanthanide series, metals of the actinide series, an mixtures thereof.

46. The method of claim 45 wherein said metal is selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.

47. The method of claim 46 wherein said catalytic metal is selected from the group consisting of Fe, Ni, and Co, and mixtures thereof.

48. The method of claim 45 wherein said catalytic metal is selected from the group consisting of Cr, Mo, and W.

49. The method of claim 42 wherein said catalytic metal is deposited in situ on each nanotube as a metal atom cluster.

50. The method of claim 49 wherein sad metal atom cluster has from about 10 to about 200 metal atoms.

51. The method of claim 42 wherein said catalytic metal is deposited as preformed nanoparticles.

52. The method of claim 51 wherein said catalytic Mo.

53. The method of claim 42 wherein said catalytic metal is deposited in the form of a metal precursor selected from the group consisting of salts, oxides and complexes of said metal.

54. The method of claim 42 wherein said catalytic metal is deposited by evaporating metal atoms and allowing them to condense and coalesce on said open nanotube ends.

55. The method of claim 54 wherein said evaporation is effected by heating a wire or wires containing said catalytic metal.

56. The method of claim 54 wherein said evaporation is effected by molecular beam evaporation.

57. The method of claim 42 wherein gaseous source of carbon is selected from the group consisting of hydrocarbons and carbon monoxide.

58. The method of claim 57 wherein said hydrocarbon is selected from the group consisting or alkyls, acyls, aryls and aralkyl having 1 to 7 carbon atoms.

59. The method of claim 58 wherein said hydrocarbon is methane, ethane, ethylene, acetylene, acetone, propane, propylene and mixtures thereof.

60. The method of claim 42 wherein said localized energy is provided by a laser beam.

61. The method of claim 42 wherein said localized energy is provided by a source selected from the group consisting of a microwave generator, an R-F coil and a solar concentrator.

62. The method of claim 42 wherein said end is heated to a temperature in the range of about 900°

C. to about 1100°

C.

63. A composition of matter comprising at least about 80% by weight of single-wall carbon nanotubes.

64. The composition of claim 63 comprising at least about 90% by weight of single-wall carbon nanotubes.

65. The composition of claim 63 comprising at least about 95% by weight of single-wall carbon nanotubes.

66. The composition of claim 63 comprising at least about 99% by weight of single-wall carbon molecules.

68. The article of claim 67 comprising at least about 90% by weight of single-wall nanotubes.

69. The article of claim 67 comprising at least about 95% by weight of single-wall nanotubes.

70. The article of claim 67 comprising at least about 99% by weight of single-wall nanotubes.

71. The article of claim 67 in the form of a paper-like material.

67. A substantially two-dimensional article comprising at least about 80% by weight of single-wall carbon nanotubes.

72. A tubular carbon molecule having the following structure:

73. The molecule of claim 72 wherein said graphene sheet has a configuration that corresponds to a (n,n) single-wall carbon nanotube.

74. The molecule of claim 72 wherein said molecule has a length from about 5 to about 1000 nm.

75. The molecule of claim 74 wherein said molecule has a length of from about 5 to about 500 nm.

76. The molecule of claim 72 wherein n is 0 to 12.

77. The molecule of claim 72 further comprising at least one endohedral species.

78. The molecule of claim 77 wherein said endohedral species is selected from the group consisting of metal atoms, fullerene molecules, other small molecules and mixture thereof.

79. The molecule of claim 78 comprising a (10,10) single-wall nanotube containing at last one endohedral species selected from the group consisting of C₆₀, C₇₀, or mixtures thereof.

80. The molecule of claim 79 wherein said C₆₀ or C₇₀ additionally contains an endohedral substituent selected from the group consisting of metal atoms and metal compounds.

106. A bistable, nonvolatile memory bit comprising the endohedrally-loaded tubular carbon molecule of claim 77.

107. The memory bit of claim 106 wherein the tubular carbon molecule is formed from a (10,10) type nanotube and the endohedral species is a C₆₀ or C₇₀ fullerene molecule.

108. A bistable, nonvolatile memory device comprising the memory bit of claim 106, means for writing to said bit and means for reading said bit.

109. The memory device of claim 108 wherein said means for writing comprises a nanocircuit element adapted to direct a voltage pulse of positive or negative polarity at said bit to cause said endohedral species to move from a first end to a second end of said bit.

110. The memory device of claim 108 wherein said means for reading said bit comprises

(a) a first nanocircuit element adapted to be biased at a first voltage (V_Read) and spaced from a read end of said bit to form a first gap therebetween;

and

(b) a second nanocircuit element adapted to be biased to ground voltage (V_G) and spaced from said read end of said bit to form a second gap, whereby the presence of said endohedral species is unambiguously determined by the presence of current tunneling across said first and second gaps.

81. A macroscopic molecular array comprising at least about 10⁶ single-wall carbon nanotubes in generally parallel orientation and having substantially similar lengths in the range of from about 5 to about 500 nanometers.

82. The array of claim 81 wherein said nanotubes are of the same type.

83. The array of claim 82 wherein said nanotubes are of the (n,n) type.

84. The array of claim 83 wherein said nanotubes are of the (10,10) type.

85. The array of claim 83 wherein said nanotubes are of the (m,n) type.

86. The array of claim 81 wherein said nanotubes are of different types.

87. The array of claim 81 further comprising a substrate attached to one end of said array and oriented substantially perpendicularly to the nanotubes in said array.

88. The array of claim 87 wherein said substrate is a bucky paper surface.

89. The array of claim 87 wherein said substrate is a metal layer selected from the group consisting of gold, mercury and indium-tin-oxide.

90. The array of claim 86 wherein a central portion of nanotubes are of the (n,n) type and an outer portion of nanotubes are of the (m,n) type.

104. A solar cell for converting broad spectrum light energy into electrical current comprising a molecular array according to claim 81 as the photon collector.

105. The solar cell of claim 104 additionally comprising a photoactive dye coupled to the upper ends of the nanotubes in said array.

111. A microporous anode for an electrochemical cell comprising a molecular array according to claim 81.

112. A lithium ion secondary battery comprising the anode of claim 111, a cathode comprising LiCoO₂ and an aprotic organic electrolyte wherein a fullerene intercalating compound (FIC) of lithium forms at the anode under charging conditions.

114. The apparatus of claim 113 wherein said means for locally heating comprises a laser.

115. The apparatus of claim 113 enclosed in a growth chamber maintained at a vacuum by evacuation means.

116. The apparatus of claim 115 further comprising a vacuum feed lock zone through which said continuously produced carbon fiber is passed and a take-up roll at atmospheric pressure.

118. The composite material of claim 117, wherein said matrix comprises a polymer.

119. The composite material of claim 118, wherein said polymer comprises a thermosetting polymer.

120. The composite material of claim 119, wherein said thermosetting polymer is selected from the group consisting of phthalic/maelic type polyesters, vinyl esters, epoxies, phenolics, cyanates, bismaleimides, and nadic end-capped polyimides.

121. The composite material of claim 118, wherein said polymer comprises a thermoplastic polymer.

122. The composite material of claim 121, wherein said thermoplastic polymer is selected from the group consisting of polysulfones, polyamides, polycarbonates, polyphenylene, oxides, polysulfides, polyether ether ketone, polyether sulfones, polyamide-imides, polyetherimides, polyimides, polyarylates, and liquid crystalline polyesters.

123. The composite material of claim 117, wherein said matrix comprises a metal.

124. The composite material of claim 117, wherein said matrix comprises a ceramic.

125. The composite material of claim 117, wherein said matrix comprises a cermet.

126. The composite material of claim 117, wherein said carbon nanotube material comprises tubular carbon nanotube molecules.

127. The composite material of claim 117, wherein said carbon nanotube material comprises ropes up to about 10³ SWNTs.

128. The composite material of claim 117, wherein said carbon nanotube material comprises fibers of greater than 10⁶ SWNTs.

129. The composite material of claim 126, 127, or 128, further comprising an additional fibrous material.

130. The composite material of claim 126, 127, or 128, wherein said carbon nanotube material is modified to interact with said matrix material.

132. The method of claim 131, wherein said carbon nanotube material is combined with said material precursor before said step of forming.

133. The method of claim 131, wherein said carbon nanotube material is combined with said matrix material precursor during said step of forming.

134. The method of claim 131, wherein said carbon nanotube material is combined with said matrix material precursor immediately after said step of forming.

135. The method of claim 131, wherein said matrix material precursor is caused to flow around a pre-formed arrangement of said carbon nanotube material.

137. The method of claim 136, wherein said fibrous materials are arranged in a two-dimensional sheet, and some portion of the said carbon nanotube material is oriented in a direction other than parallel to said sheet.

138. The method of claim 131 or 136 wherein said carbon nanotube material comprises tubular carbon nanotube molecules.

139. The method of claim 131 or 136, wherein said carbon nanotube material comprises ropes of up to about 10³ SWNTs.

140. The method of claim 131 or 136, wherein said carbon nanotube material comprises fibers of greater than 10⁶ SWNTs.

142. The three-dimensional structure of claim 141, wherein said single-wall carbon nanotubes have multifunctional derivatives on their end caps.

143. The three-dimensional structure of claim 141, wherein said single-wall carbon nanotubes have multifunctionl derivatives at multiple locations on said single-wall carbon nanotubes.

144. The three-dimensional structure of claim 141, wherein said single-wall carbon nanotubes are assembled as a result of van der Waals attractions.

145. A three-dimensional structure of claim 141, which has electromagnetic properties.

146. The three-dimensional structure of claim 145, wherein said electromagnetic properties are determined by a functionally-specific agent.

147. A three-dimensional structure of claim 141, which is symmetrical.

148. A three-dimensional structure of claim 141, which is not symmetrical.

149. A three-dimensional structure of claim 141, which has biological properties.

150. A three-dimensional structure of claim 149, which operates as a catalyst for biochemical reactions.

151. A three-dimensional structure of claim 149, which interacts with living tissue

152. A three-dimensional structure of claim 149, which serves as an agent for interaction with functions of a biological system.

154. The light harvesting antenna of claim 153, wherein said at least one single-wall carbon nanotube forms a Schottky barrier.

155. An array of light harvesting antennas of claim 153.

156. The array of light harvesting antennas of claim 155, wherein said array is formed by self-assembly.

158. The molecular electronic component of claim 157, wherein said molecular electronic component is a bridge circuit for providing full wave rectification, said bridge circuit comprising:

four single-wall carbon nanotubes, each of said four single-wall carbon nanotubes forming one edge of a square and linked to two of four buckyballs, each of said four buckyballs located at a corner of said square.

159. The bridge circuit of claim 158, wherein said buckyballs and single-wall carbon nanotubes are deed to include functionally specific linking agents.

160. A molecular electronic component of claim 157, which is a fullerene diode.

162. The nanoscale manipulator of claim 161, which is nanoforcepts.

91. A macroscopic carbon fiber comprising at least about 10⁶ single-wall carbon nanotubes in generally parallel orientation.

92. The fiber of claim 91 comprising at least about 10⁹ single-wall carbon nanotubes.

93. A composite fiber comprising a plurality of the fibers of claim 91.

94. A molecular template array for growing continuous length carbon fiber comprising a segment of the fiber of claim 91.

95. The fiber of claim 91 having a length of at least 1 millimeter.

96. The fiber of claim 91 wherein a substantial portion of said nanotubes are of the (n,n) type.

97. The fiber of claim 91 wherein all of said nanotubes are not of the same type.

98. A composite article of manufacture comprising a matrix material selected from the group consisting of metals, polymers, ceramics and cermets, said matrix having embedded in at least a portion thereof a property enhancing amount of the carbon fibers of claim 91.

99. The composite article of claim 98 wherein said property is structural, mechanical electrical, chemical, optical, or biological.

100. A high voltage power transmission cable wherein at least one conductor comprises a continuous carbon fiber according to claim 96.

101. The power transmission cable of claim 100 wherein both a central conductor and a coaxially disposed outer conductor are formed from said carbon fiber and an insulating layer is disposed therebetween.

102. The power transmission cable of claim 101 wherein said insulating layer is an air space.

103. The power transmission cable of claim 101 wherein said insulating layer comprises a material selected from the group consisting of insulating carbon fiber made from carbon nanotubes of the (m,n) type and insulating BN fiber made from hexaboronitride nanotubes or mixtures thereof.

113. An apparatus for forming a continuous macroscopic carbon fiber from a macroscopic molecular template array comprising at least about 10⁶ single-wall carbon nanotubes having a catalytic metal deposited on the open ends of said nanotubes, said apparatus comprising:

(a) means for locally heating only said open ends of said nanotubes in said template array in a growth and annealing zone to a temperature in the range of about 500°

C. to about 1300°

C.;

(b) means for supplying a carbon-containing feedstock gas to the growth and annealing zone immediately adjacent said heated open ends of said nanotubes in said template array; and

(c) means for continuously removing growing carbon fiber from said growth and annealing zone while maintaining the growing open end of said fiber in said growth and annealing zone.

117. A composite material comprising:

(a) a matrix; and

(b) a carbon nanotube material embedded within said matrix.

131. A method for producing a composite material containing carbon nanotube material comprising:

(a) preparing a matrix material precursor;

(b) combining a carbon nanotube material with said matrix material precursor; and

(c) forming said composite material,

136. A method of producing a composite material containing carbon nanotube material comprising:

(a) preparing an assembly of a fibrous material;

(b) adding said carbon nanotube material to said fibrous material; and

(c) adding a matrix material precursor to said carbon nanotube material and said fibrous material.

141. A three-dimensional structure that self-assembles from derivatized single-wall carbon nanotube molecules comprising:

a plurality of multifunctional single-wall carbon nanotubes assembled into said three-dimensional structure.

153. A light harvesting antenna comprising:

at least one single-wall carbon nanotube conductive element, said at least one nanotube having a length selected relative to a desired current level and a desired voltage level.

157. A molecular electronic component comprising at least one single-wall carbon nanotube.

161. A nanoscale comprising at least one single-wall carbon nanotube.