MXPA00012681A - Free-standing and aligned carbon nanotubes and synthesis thereof - Google Patents

Abstract

One or more highly-oriented, multi-walled carbon nanotubes are grown on an outer surface of a substrate initially disposed with a catalyst film or catalyst nano-dot by plasma enhanced hot filament chemical vapor deposition of a carbon source gas and a catalyst gas at temperatures between 300°C and 3000°C. The carbon nanotubes range from 4 to 500 nm in diameter and 0.1 to 50&mgr;m in length depending on growth conditions. Carbon nanotube density can exceed to 104 nanotubes/mm2. Acetylene is used as the carbon source gas, and ammonia is used as the catalyst gas. Plasma intensity, carbon source gas to catalyst gas ratio and their flow rates, catalyst film thickness, and temperature of chemical vapor deposition affect the lengths, diameters, density, and uniformity of the carbon nanotubes. The carbon nanotubes of the present invention are useful in electrochemical applications as well as in electron emission, structural composite, material storage, and microelectrode applications.

Description

CARBON NANOTUBES ALIGNED AND SELFTABLE AND SYNTHESIS OF THEMSELVES FIELD OF THE INVENTION The present invention relates to a product with a substrate having one or more carbon nanotubes, a method for producing this product, and devices using the product.

BACKGROUND OF THE INVENTION Since the first observation of carbon nanotubes, numerous documents have reported studies on the performance of well-grained nanotubes, their diameter and wall thickness (single or multiple), mechanisms of growth, alignment, emission properties of electrons, nanodi spos i t i o s, theoretical predictions, and potential applications. The selective placement and growth of carbon nanotubes is necessary for future integration with conventional microelect elements as well as Ref. 125918 the development of new devices. However, limited progress in the controlled placement of nanotubes has been reported. The alignment of carbon nanotubes is particularly important to allow both fundamental studies and applications, such as cold cathode flat panel display devices, chargeable batteries, and vacuum microelectonic devices. Specifically, vertical alignment has been an important goal because of its technological importance for applications such as scanning probe microscopy and flat panel emission devices by field effect. Attempts to manipulate nanotubes for these applications have been made by post-growth or post-culture methods such as separation of a polymer resin nanotube composite, or design a nano-tube suspension using a ceramic filter. Because these techniques are difficult and labor-intensive, the alignment of nanotubes in si t u during growth has been attempted using techniques such as porous alumina membrane nanopores and laser-etched nanotraces. There are small events in obtaining alignment of carbon nanotubes over large areas until the report by Li et al., "Large-Scale Synthesis of Aligned Carbon Nanotubes," Science, 274: 1701-1703 (1996) ("Li") . Li describes the growth of carbon nanotubes aligned on mesoporous silica containing iron nanoparticles via the thermal decomposition of acetylene gas into nitrogen gas at temperatures above 700 ° C. In this method, the substrate is prepared by a sol-gel process from the hydrolysis of tea and brings it into the aqueous solution of iron nitrate. The gel is then calcined for 10 hours at 450 ° C at 10 ° 2 Torr.A silica network with relatively uniform pores is obtained with iron oxide nanoparticles embedded in the pores.The iron oxide nanoparticles then reduce to 550 ° C in 180 Torr of flow (9% H2 / N2 (110 cmVmin) for 5 hours to obtain iron nanoparticles, Later, the nanotubes are cultivated in a gas environment of a mixture of 9% acetylene in nitrogen at 700 ° C. Aligned nanotubes are along the axial direction of the pores Only nanotubes growing out of vertical pores are aligned Nanotubes which grow from iron particles on the surface and in the pored, scattered pores are In this method, the alignment of nanotubes is limited to the restriction of vertically aligned pores.In addition, the density and diameter of aligned carbon nanotubes are respectively limited in direct proportion to the amount and size of the nanotubes. iron nanoparticles and pore diameter As described in Li, a temperature lower than 700 ° C is required to decompose acetylene and induce the growth of nanotub However, this high temperature requirement limits the selection of the substrate. For example, a glass substrate is not suitable for use in this method due to its low deformation point temperature. A glass produced by Corning Incorporated (Corning, New York) has the highest knowledge of glass deformation of the display device or flat panel indicator or deformation point temperature of 666 ° C. Typically, a glass of the commercially available flat panel display or indicator device has a deformation point temperature between 500 ° C and 590 ° C. At 700 ° C, the glass substrates deform and inhibit the growth of aligned carbon nanotubes. Therefore, any substrate suitable for use with this method must have a melting point or deformation point temperature greater than 700 ° C. Terrones et al., "Controlled Production of Aligned-Nanotube Bundles", Nature, 388: 52-55 (1997) ("Terrones") describes a method for laser-induced cultivation of bundles or groups of nanotubes aligned on a substrate under high temperature conditions. A thin cobalt film is deposited on a silica plate by laser ablation and therefore is recorded with a simple laser pulse to create nano linear trajectories. The 2-amino-4,6-dichloro-s-triazine is then placed on the silica plate in the presence of argon gas in a two-phase furnace. The first oven is heated to 1,000 ° C and then allowed to cool to room temperature. The second oven is heated and maintained at 950 ° C. Although carbon nanotubes grow along the edges of worn nanotrayectors, growth occurs only on the undersurface of the substrate and in a non-vertical form. The carbon nanotubes do not grow on a superior surface of the substrate prepared in a similar way that indicates the growth of nanotubes that according to this method is dependent on gravity. Again, for the reasons discussed above, the substrate selection for this method is limited to a substrate that has either a deformation point temperature or melting point greater than 1,000 ° C. In addition, the density of nanotubes is directly limited to the number of nanotrawings recorded on the surface of the substrate. Accordingly, there is a need for a method of forming carbon nanotubes, vertically or otherwise aligned, at temperatures below 700 ° C. Similarly, a need is maintained for a substrate having carbon nanotubes vertically aligned on the substrate surface. In addition, a need remains for a method of forming individual, self-contained carbon nanotubes and a substrate with one or more individual, individual carbon nanotubes placed on the surface of the substrate. The present invention is directed to overcoming these deficiencies in the art.

DESCRIPTION OF THE INVENTION The present invention relates to a product which has a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate, (2) a plurality of substantially carbon nanotubes. aligned with a density not greater than 102 nanotubes per square millimeter of substrate, (3) one or more carbon nanotubes, where the substrate has a temperature of deformation point or melting point between approximately 300 ° C and 700 ° C, (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from the outer surface of the substrate, or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from the external surface of the substrate. Carbon nanotubes are synthesized by deposition of hot filament chemical vapor enhanced by plasma from a carbon source gas in a reduced pressure environment in the presence of a catalyst gas at temperatures as low as 300 ° C to 3000 ° C in a ratio range or volume ratio of gas from carbon source to catalyst gas from 1: 2 to 1:10. The large array growth of well aligned carbon nanotubes having a diameter between 4 to 500 nm occurs on a substrate coated with a thin film of metal catalyst. The freestanding carbon nanotubes are developed on metal catalyst nanodots placed on the substrate. The present invention provides a method for forming carbon nanotubes, vertically or otherwise aligned, at temperatures below 700 ° C. In addition, products made in accordance with this method provide a substrate which has carbon nanotubes vertically aligned on the substrate surface. In addition, a product made in accordance with the method of the present invention includes a substrate having freestanding carbon nanotubes., indi iduals. Yet, a product made in accordance with the method of the present invention includes a substrate having one or more individual freestanding carbon nanotubes placed on the surface of the substrate. The products of the present invention are useful in electrochemical applications as well as in applications of electron emission, structural compound, material storage, and application of my readings.

BRIEF DESCRIPTION OF THE DRAWINGS Figures 1A-B are scanned images showing alignment of carbon nanotubes growing over a large area of Ni poly icri t substrate. Figure 2 is a scanned image of a scanning electron microscope micrograph showing the growth of carbon nanotubes at a high plasma intensity under the conditions listed in Table 1 (b). Figure 3 is a scanned image showing carbon nanotubes with higher aspect ratios synthesized with a higher plasma intensity than that used for the carbon nanotubes shown in Figure 2. Figure 4 is a scanned image showing a group of Carbon nanotubes extracted from a Ni substrate directly onto a Cu TEM grid, with the insert showing a cross-sectional image of a portion of a single, multi-walled carbon nanotube structure. Figures 5A-B are scanned images showing carbon nanotubes aligned substantially perpendicular to a substrate on growing conditions of large areas as listed in Table 2. Figure 5B is an enlarged view of Figure 5A along a length of detached edge to show diameters, length, straightness, and uniformity of carbon nanotubes. Figures 6A-C are scanned images showing the morphology of the electron microscope surface of the nickel catalyst layers. Figure 6A illustrates the effects of plasma of NH3 recorded for 3 minutes. Figure 6B illustrates the effects of the N2 plasma that is recorded for 3 minutes. Figure 6B shows a smooth catalyst surface subjected to electronic deposition. Figures 7A-B are scanned images showing the carbon nanotubes grown under the conditions listed in Table 2. Figure 7B is an enlarged view of Figure 7A to show carbon nanotube diameters and distributions. Figure 8A is a scanned image showing thinner carbon nanotubes grown on glass covered with thinner nickel (15 nm) under the conditions listed in Table 2. Figure 8B is a scanned image showing the carbon nanotube with diameters of about 20 nm grown under the conditions listed in Table 2. Figures 9A-B are scanned images showing the interior and wall structures of a typical thin carbon nanotube, wherein Figure 9A is a cross-sectional view and Figure 9B is a plan view. Figure 10 is a scanned image showing the growth of the large area of carbon nanotubes well aligned on glass. Figure 11 is a scanned image showing carbon nanotubes well aligned on silicon. Figure 12 is a scanned image showing very short carbon nanotubes grown for only 2 minutes. Figure 13 is a scanned image showing open ended carbon nanotubes recorded by HN03 for 1 minute. Figure 14 is an explored image showing carbon nanotubes subjected to electronic deposition of Ar iron. Figure 15 is a scanned image showing a side view of well aligned carbon nanotubes grown at an angle to the substrate. Figure 16 is a scanned image showing a top view of the carbon nanotubes of Figure 15. Figure 17A is a scanned image showing carbon nanotubes grown on the edge of a metal pad. Figure 17B is a scanned image showing a region similar to Figure 17A in which the carbon nanotubes are broken. Figures 18A-F are a series of images exhibiting various observation angles of carbon nanotube obelisks grown from a configured array of catalyst nanopoints. Figure 18A is a perspective view of a plurality of configured arrangements. Figure 18B is a top view of the configured arrays of Figure 18A at a reduced magnification. Figure 18C is a perspective view of a configured array. Figure 18D is a top view of a configured array. Figure 18E is a perspective view to an enlarged magnification of the configured array of Figure 18C. Figure 18F is a perspective view of separate carbon nanotube obelisks. Figure 19 is a scanned image showing an elevation view of a carbon nanotube obelisk. Figure 20 is a partial top view of a field-effect emission display apparatus of the present invention. Figure 21 is a perspective view of a probe for an electron scanning microscope of the present invention. Figure 22 is a schematic view illustrating an example of an electron scanning microscope of the present invention. Figure 23 is a schematic drawing illustrating an example of the basic construction of a battery of the present invention. Figure 24 is a schematic drawing illustrating a fuel cell of the present invention. Figure 25 is a schematic drawing illustrating an electromagnetic interference field placed between a source of electromagnetic interference and an electronic component.

Figure 26 is a schematic drawing illustrating a microelectrode of the present invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a product which includes a substrate and one or more hollow core carbon nanotubes originating from a surface of the substrate. When the product has more than one carbon nanotube, the carbon nanotubes are well aligned and can be attached or extended either perpendicularly or non-perpendicularly from the substrate surface. The embodiments of the product of the present invention include the substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate, (2) a plurality of substantially carbon nanotubes of carbon. a density not greater than 102 nanotubes per square millimeter of a substrate, (3) one or more carbon nanotubes, where the substrate has a melting point or deformation point between about 300 ° C and 700 ° C, ( 4) a plurality of substantially aligned carbon nanotubes that originate and extend outwardly from the outer surface of the substrate, or (5) one or more freestanding carbon nanotubes that originate or extend outwardly from the outer surface of the substrate. substrate As shown in Figures 1-19, the carbon nanotubes of the present invention are substantially concentric tubules. The nanotubes have diameters ranging from 4 to 500 nm and lengths up to 50 μm. Preferably, carbon nanotubes which are longer than 20 μm have a diameter of at least 50 nm to maintain alignment. Depending on the growth conditions, the carbon nanotubes can be either freestanding nanotube obelisks having a sharp tapered carbon tip or end or a long array of well-aligned nanotubes which have a layer located distally from the substrate. Large arrays of carbon nanotubes have densities of 10d to 108 nanotubes per square millimeter of substrate. The layer comprises a metal alloy or metal catalyst material of iron, cobalt, nickel, or an alloy of iron, cobalt, or nickel. The catalyst material and its function are described further below. In one embodiment of the present invention, the ends and layers are removed to reveal the open ended carbon nanotubes. It is contemplated that a wide variety of electrical or non-electrically conductive substrates can be used with the present invention. For example, suitable substrates include glass, quartz, silicon, platinum, iron, cobalt, nickel, an alloy of iron, cobalt, or nickel, a ceramic, or a combination thereof. Particularly useful substrates are glass panels and silicon plates. It is important to recognize that the most important property of the substrate is that the temperatures of the deformation point and / or boiling point of the substrate are above the growth temperature of the carbon nanotube. With the present invention, the substrate must have temperatures of the deformation point and / or melting point of at least about 300 ° C. As described in Li, the substrates used in the prior art should have temperatures of the deformation point and / or melting point in excess of 700 ° C. Accordingly, a product of the present invention and the substrate here have a temperature of the point of deformation or melting point between 300 ° C and 700 ° C. Such substrates include flat panel display glass substrates, which have deformation point and / or melting point temperatures of 666 ° C and below, may be used. Certain ceramics, such as LaA103, A1203, and Zr02, YSZ, and SrTi03 have melting point temperatures of about 3000 ° C and are useful as substrates used in high temperature environments. In the present invention, carbon nanotubes are growing only on one surface of a substrate by providing the substrate in a reduced pressure environment containing a carbon source gas and a catalyst gas and exposing the substrate to a plasma under effective conditions to cause the formation and growth of one or more carbon nanotubes on the substrate. This is defined as chemical plasma vapor deposition of improved plasma hot filament (for its acronym in English, PE-HF-CVD). Accordingly, the present invention is also directed to products which have carbon nanotubes that originate and extend outward from an outer surface of the substrate. Prior to the growth of the carbon nanotubes by PE-HF-CVD, the substrates are placed in a deposition chamber at a reduced pressure (<; 6 x 10"6 Torr) and coated with the metal or metal catalyst alloys described above Any metal catalyst film of at least about 15 nm in thickness or one or more metal catalyst nanodots of approximately 150A in thickness is deposited on The catalyst film is deposited by electronic deposition of radiofrequency magnetron.The catalyst nanopoints are deposited by evaporation of electron beams, thermal evaporation, or magnetron electron deposition.Shortly, the diameters of the carbon nanotube Increasing result are directly related to the thickness of the catalyst film.Variable thickness of the catalyst film, the diameter of the carbon nanotubes can be controlled.Although the thickness of nanodots can have a similar effect on the diameter of the resulting nanotube, the thickness is less controlled than the film. To produce the products of the present invention, the coated substrates are placed in a reduced pressure CVD chamber containing a carbon source gas and a catalyst gas and then exposed to a plasma under conditions effective to cause formation and growth of one or more carbon nanotubes on the surface of the substrate. Generally, the CVD chamber has a pressure between about 0.1 to about 100 Torr, preferably about 1 to about 20 Torr. Because the growth of the carbon nanotube is induced by improved plasma by chemical vapor deposition of the carbon source gas, the warm atmosphere of the CVD chamber can be maintained at a temperature between about 300 ° C and roughly 3000 ° C. As a result of the low temperature requirement, various substrates having relatively low point of deformation or melting point temperatures as low as 300 ° C can be used in the present invention. As indicated above, the growth of carbon nanotubes can occur at very high temperatures and is restricted only by the temperature of the melting point of the selected substrate. The upper temperature limit of the growth of carbon nanotubes is estimated to be about 3000 ° C, which corresponds to the melting point temperature of the highly known ceramic substrate, as described above. The growth time depends on the length requirement of nanotubes. Normally, it is between 1 - 10 minutes, which yields a length of 0.1 - 20 μm. The growth durations can be extended up to 5 hours depending on the lengths of the desired carbon nanotube. The carbon source and catalyst gases flow through the CVD chamber with a ratio or volume ratio of gas from the carbon source to the catalyst gas ranging from 1: 2 to 1:10 at a pressure maintained between approximately 0.1 a approximately 100 Torr at a temperature between approximately 300 ° C to 3000 ° C. The gas from the carbon source can be selected from linear unsaturated, branched, or hydrogen and cyclic carbon compounds having up to six carbon atoms which are gases at the deposition pressure. For example, very pure acetylene (99.99% purity), ethylene and benzene, preferably acetylene, can be used as the carbon source gas of the present invention. The catalyst gas is ammonia (99.99% purity) at CVD temperatures below 700 ° C. At CVD temperatures above 700 ° C, the catalyst gas may be ammonia, nitrogen (99.99% purity), or a combination thereof. Ammonia is the most preferred catalyst gas of the present invention. Preferably, the carbon source and catalyst gases are introduced into the CVD chamber simultaneously or the catalyst gas is introduced prior to the gas from the carbon source.

The carbon nanotubes are synthesized with the diameter, length, density of the site, and controlled growth angle. The intensity of the plasma can be varied to determine the ratios or aspect ratios of the nanotube by diameter and length, and varies from both the distributions of both site and height distributions. The vertical or non-vertical growth of the carbon nanotubes is independent of the topography of the substrate surface and can be controlled by the displacement of the substrate angle in the CVD chamber with respect to the orientation of the electric field of the plasma generator. These low temperature growth conditions are suitable for electron emission applications, such as cold cathode flat panel display devices that require the emitters of carbon nanotubes to grow substantially perpendicular to a surface of the glass substrate. . However, the growth of carbon nanotubes at the lower temperature has more defects or discontinuities. These discontinuities provide a diffusion path to the nucleotide of nanotubes. There is a desire to manufacture carbon nanotubes with limited defects, they can be used at high or higher growth temperatures. The mechanism of growth of aligned carbon nanotubes is attributed in the literature to that it is a restriction of the pores in mesoporous silica or the trajectories engraved with laser in silica. In the present invention, the alignment of the carbon nanotubes can not be due to the pores or engraved trajectories since there are no pores or trajectories recorded on the glass substrates, as shown in Figures 5A-B, 10, 15, 17A-B, and 18C, E, and F. The fastest alignment is due to a nanotube nucleation process catalyzed by the catalyst gas (e.g., ammonia) and the catalyst or nanopoint layer (e.g., nickel). In the presence of the catalyst gas, each metal catalyst layer efficiently catalyzes the continuous synthesis of the carbon nanotubes. With the growth of carbon nanotubes, the layer remains at the far end of each carbon nanotube. This alignment and thickness of the carbon nanotubes can be determined by the orientation and respective size of the initial catalytic centers. If desired, the metal catalyst layers can be removed by subjecting the carbon nanotubes to any etched HN03 solution or electron deposition by Ar iron to open the far ends. In some applications, a single carbon nanotube or configurations with controlled site density is desired, which can be accomplished by selective deposition of the catalyst nanopoints. In the present invention, the carbon nanotubes grown from the metal catalyst nanodots are obelisks having sharp, tapered carbon ends and have round base diameters of approximately the same as the nanodots. The height of the nanotube depends on the growth time and thickness of nanopoints. The ends can be removed as well as providing an open ended nanotube by placing the nanotubes in a reaction chamber and exposing the nanotubes to oxygen and heat at approximately 400 ° C for about 0.5 hours.

A filler can be placed inside the carbon nanotubes through the open ends or by the structural discontinuities. For example, filler such as hydrogen, lithium ions, bismuth, lead telluride, bismuth trithelide, or a pharmacological agent, to name but a few, can be inserted into the nucleotide of the nanotube by physical or electrochemical methods. If desired, the open ends of the carbon nanotubes can be closed or sealed by electronic magnetron deposition or electrochemical deposition of a confining material, such as a metal. Now, referring to Figure 20, a conventional flat panel display or indicator device or field display emission device 100 has a base plate 102, a face plate 104 coated with phosphor spaced apart, and an array of electron emitter 106 placed on the base plate 102 to emit electrons that collide and thereby illuminate the phosphor coating. The base plate 102, the front plate 104 and the emitter array 106 are placed in a vacuum environment. The emitter 106, which is operably connected to a source that generates electrons, has a sharp end 108, known as a Spindt end, to emit electrons. However, these emitters 106 have certain disadvantages because they have a relatively short wear life, have a low emission density due to the limits of the existing lithographic technology, and are relatively expensive. The products of the present invention comprise large arrays of well-aligned carbon nanotubes as shown in, for example, Figures 1, 2, 5, 7, 10, 11, and 18B, can be used to replace the array combination of the base plate / emitter 102 and 106. Since carbon nanotubes can be produced highly aligned and perpendicular to the substrate, display devices or field emission indicators can be manufactured using such arrays as emitters. In addition, as described in Schmid et al., "Coal Nanotubes Are Coherent Electron Sources," Appl. Phys. Lett. , 70 (20): 2679-2680 (1997) ("Schmid"), Collins et al., "A Simple And Robust Electron Beam Source From Carbon Nanotubes", Appl. Phys.

Lett. , 69 (13): 1969-1971 (1996), and Rinzler et al., Unraveling Nanotubes: Field Emission From an Ato ic Wire ", Science, 269: 1550-1553 (1995) (" Rinzler "), all of these Incorporated here as a reference, carbon nanotubes emit electrons in the same way as Spindt ends during the operable connection to a source that generates electrons.Canon nanotubes can not only increase the life of the emitter, they improve contrast and brilliance also due to the density of the large nanotube Referring to Figures 19, 21, and 22, and generally to Figures 1-18, the products of the present invention can be used as a probe for an electron scanning microscope, as shown in FIG. indicates in Rinzler An electron scanning microscope 200 of the present invention comprises a vacuum chamber 202 capable of receiving a specimen 204, an electron source 206 to produce electrons, a probe 208 which is disposed operably inside of the vacuum chamber 202 to emit and direct the electrons to and scan the specimen 204, a detector 210 operably placed within the vacuum chamber 202 to collect the radiation exiting the specimen 204 as a result of scanning by the probe 208 to producing an output signal, and an indicator display 212 operably connected to the detector 210 to receive the output signal and resulting in the display of an image of the area of the specimen 204 scanned by the probe 208. Referring to FIGS. 1-5B, 7 -19 and 21, probe 208 is a product of the present invention having a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a deformation point temperature or boiling point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes originating and extending outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate. Preferably, the probe 208 is a product of the present invention comprising a substrate 214 having an outer surface 216 and a freestanding carbon nanotube 218 that originates and extends from the outer surface 216 of the substrate 214. Selective placement and growth of a simple or single, self-supporting carbon nanotube of a single catalyst nanopoint, according to the method of the present invention as previously described, can produce probe 208. Referring to Figure 21, and generally to Figure 19 , a single, self-supporting carbon nanotube 218, which originates and extends from the outer surface 216 of a substrate 214 is operably connected to the electron source 206. The substrate 214 is selected from an electrically conductive material, which is connectable to the electron source. In operation, specimen 204 is placed inside vacuum chamber 202, and chamber 202 is evacuated. The microscope 200 scans the specimen 204 with a thin probe of electrons that are emitted from the probe 208. The electrons are produced from the electron source 206, which can be a source of emission by electron field effect (not shown) and suitable acceleration electrodes (not shown), such as an electron gun (not shown). The electrons that are transmitted through the specimen 204 are collected by the detector 210 to provide the output signal. For example, the detector 210 may comprise a phosphor screen (not shown) with a photomultiplier (not shown) to detect light from the screen. This output signal is used to modulate the beam of the display 212, such as a cathode ray tube, which is scanned in synchronism with the probe 208, so as to cause the display screen 212 to display a configuration of which depends on the structure of the scanned portion of the specimen 204. Alternatively, instead of collecting the transmitted electrons, the secondary radiation (e.g., x-rays or electrons) emitted from the specimen 204 as a result of bombardment by the electrons of the probe 208, can be detected to provide the output signal. In a microscope, the electron thin probe or carbon nanotube 218 must be very thin, such as to illuminate only a small region of specimen 204, to allow small characteristics of specimen 204 to be examined. The production of a fine electron probe requires an electron source 206 having a very small electron emission area such as, for example, a source of emission electrons by field effect. The magnets 220 can be operably placed in the vacuum chamber 202 to foci or alter the emitted electron probe. The carbon nanotubes produced in accordance with the present invention are such electron emitters. The products of the present invention can also be used to form alkaline metal ion batteries, such as lithium batteries. As shown in Figures 23, the battery 300 comprises an anode 302, a cathode 304, an isolator 306 positioned between the anode 302 and the cathode 304, and an electrolyte 308. At least one of the anode 302 and the cathode 304, preferably both comprise a product of the present invention having a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a deformation point or melting point temperature between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes originating and extending outward from an external surface of the substrate; or (5) one or more of the freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate. Preferably, the product has a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of the substrate. Here, the substrate comprises an electrically conductive material, and the carbon nanotubes have at least one diffusion path to the hollow core of the nanotubes. As reported in Gao et al., "Electrochemical Intercalate ion of S ingle-walled Carbon Nanotubes with Lithium", Che. Phys. Let t. , (in press) ("Gao") the alkali metals can be electrochemically intercalated in the hollow nuclei of carbon nanotubes. Gao also reports that lithium can be reversibly intercalated from nanotubes in the range of 100-400 mAh / g. In the present invention, the lithium ions can be intercalated in the carbon nanotubes of the anode 302 by charging the battery 300. Although not required, the carbon nanotubes of the product can have open ends to provide the diffusion path of the metal, as it is shown in Figure 13. Preferably, carbon nanotubes have high structural defects or discontinuous densities in the walls. As previously described, carbon nanotubes grow at low growth temperatures (eg, 300 ° C to 400 ° C) by PE-HF-CVD have such structural discontinuities. These structural discontinuities provide highly active surface areas and numerous diffusion trajectories to the nanotube core by metal diffusion. It is not necessary for carbon nanotubes that have discontinuities to be open ended, since the diffusion of more metal occurs through the discontinuities. In the present invention, the cathode 304 functions to assist conduction for current collection, and the anode 302 functions as the host material for the lithium ions. Since the anode 302 and / or the cathode 304 comprises well aligned carbon nanotubes, the electrolyte 308 easily penetrates the nanotubes, which act as electrodes. As a result, the impedance of the battery 300 is decreased, the efficiency of the charge discharge is improved over conventional batteries, and secondary reactions during charging and discharging are prevented. Thus, the battery 300 of the present invention has a high capacity and a long life cycle. When the cathode 304 comprises the product of the present invention having intercalated lithium ions, a higher collector capacity can be achieved. As a result, the utilization of the cathode 304 can be increased to produce a high capacity lithium battery 300. The products of the present invention having carbon nanotubes substantially aligned and oriented substantially perpendicular to the substrate are preferred. By using such compounds, the electrolyte 308 can penetrate the nanotubes much easier. This results in the 300 battery that is enabled for fast loading and unloading. At anode 302, lithium can be placed on the surfaces of carbon nanotubes and intercalated in the nanotubes, whereby deposition of dendritic lithium metal is prevented and results in the battery 300 having a higher capacity . Also, when the products of the present invention are used as an anode 302 for intercalating and intriguing lithium ions, a high capacity anode 302 is formed. Again referring to Figure 23, anode 302 and cathode 304 are placed in electrolyte 308 held in a housing 310 opposite each other through insulator 306. Isolator 306 is provided. to prevent internal shorts due to contact between anode 302 and cathode 304. Anode 302 and cathode 304 respectively may comprise the products shown in Figures 1-19. An anode terminal 312 and a cathode terminal 314 are electrically connected to the substrates of the respective product comprising the anode 302 and the cathode 304. The anode terminal 312 and the cathode terminal 314 can be used by at least a portion of the cathode. housing 310. When a lithium battery 300 of the present invention is assembled, the anode 302 and the cathode 304 must be dehydrated and dried sufficiently. For example, dehydration can be carried out by heating under reduced pressure. The carbon nanotubes serve as collection electrodes of the anode 302 and the cathode 304. The nanotubes function to efficiently supply a current to be consumed by the electrode reaction during charging and discharging or to collect the current generated by the electrode reaction.

The insulator 306 functions to prevent internal shorts between the anode 302 and the cathode 304, and may function to maintain the electrolyte 308. The insulator 306 must have pores that allow the movement of lithium ions, and must be insoluble and stable in the electrolyte 306. Thus, examples of materials that should be used for insulator 306 include glass, polyolefins, such as polypropylene and polyethylene, inorganic polymers, and materials having a nonwoven and micropore structure. A metal oxide film having micropores and a resin film which is composed of a metal oxide can also be used. An electrolyte solution was prepared by dissolving the electrolyte 308 in a solvent. Examples of electrolytes 308 include acids, such as H2SO4, HCl, and HN03, salts comprising lithium ions and Lewis acid ions (BF4", PF6", C104", CF3S03", and BPh4"), and mixtures of salts thereof Salts may also be used which comprise cations such as sodium ion, calcium ion, and tetraalkylammonium ion, and the ions of Lewis acid These salts can be sufficiently dehydrated and deoxidized by heating under reduced pressure Examples of solvents which are useful for electrolyte 308 include acetonitrile, benzonitrile, propi 1 carbonate, ethylene carbonate, dimethylcarbonate, diethyl carbonate, dimethyl formamide, tetrahydrofuran , nitrobenzene, dichloroethane, dietary toxin, 1,2-dimetoxyethane, chlorobenzene, ga-butyrolactone, dioxolane, sulfolane, nitromethane, 2-methyl-1-trahydrofuran, 3-propylsidone, sulfur dioxide, phosphoryl, thionyl chloride, sulfuryl chloride, and solvent mixture thereof These solvents can be dehydrated by activated albumin, molecular sieves, phosphorus pentaoxide, or calcium chloride. Solvents are also subjected to impurity removal and dehydration by distillation in coexistence with an alkali metal in an inert gas. To prevent the dispersion of electrolyte 308, electrolyte 308 can be formed in a gel. The polymers which absorb the solvent from the electrolyte 308 and dilate it can be used as a curing agent. For example, such polymers include poly (ethylene oxide), poly (vinyl alcohol), polyacrylamide, and the like. The products of the present invention can be used to form energetic cells. An energy cell is a device for the direct conversion of chemical energy from a fuel into electrical energy. There are several constructions of energy cell devices, such as energetic cells, groups or stacks of energetic cells, and energetic cell power plants which use hydrogen as the fuel for the respective energy cell device. As is well known, an exothermic chemical reaction takes place in these energy cell devices between hydrogen and an oxidant, for example, oxygen, resulting in the formation of water as the reaction product and the generation of desired electricity. The incidental release of thermal energy exhibited as sensible heat is typically removed from the energy cell. During the previous reaction, hydrogen and oxidant are consumed by the energy cell. In order for the energy cell device to continue its operation, hydrogen and oxidant must be supplied at any respective rates of consumption. In some applications of the energy cell, hydrogen is stored in tanks or similar containers in its gaseous or liquid state in its pure form or in combination with inert substances. However, such containers are generally relatively large and heavy, and problematic when the storage space and / or weight of the payload are limited. Therefore, there is an advantage when large quantities of hydrogen gas can be stored in relatively light weight containers, compact. Referring to Figure 24, an energy cell 400 of the present invention comprises a housing 402, two gas diffusion electrodes, an anode 404 and a cathode 406, placed within the housing 402 and respectively form a side anode 408 and a side cathode 410, an electrolyte impregnated matrix or an ion exchange membrane 409 positioned between and in electrical contact with the electrodes 404 and 406, an electrically and operably external circuit 412 connecting the anode 404 to the cathode 406 and a hydrogen storage unit 414 comprising the products 416 of the present invention placed within an enclosure 418 which is operably connected to the lateral anode 408. A catalyst layer is disposed on the surfaces opposite the electrolyte of the respective electrodes 404 and 406. In the operation of the energy cell 400, hydrogen gas is fed into the back of anode 404, and oxygen gas geno is fed into the back of the cathode 406. The respective gases diffuse through the electrodes 404 and 406 and react at the catalyst sites to produce electricity, heat, and humidity. On the lateral anode 408 of the energy cell 400, hydrogen is oxidized electrochemically to yield electrons according to the reaction: 2H2? 4H + + 4 eJ The electric current when generated is conducted from the anode 404 through the external circuit 412 to the cathode 406. At the lateral cathode 410 of the energy cell 400, the electrodes are electrochemically combined with the oxidant according to the reaction : 02 + 4HT + 4e "- 2H? 0 The related flow of the electrons through the electrolyte completes the circuit ... Referring additionally to the Figures 1-19, the hydrogen storage unit 414 comprises the enclosure 418 and the products 416 of the present invention having a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of carbon nanotubes substantially aligned with a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an outer surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outward from an outer surface of the substrate. Carbon nanotubes have a hollow core and at least one diffusion path within the nucleus. Preferably, the product 416 has plurality of carbon nanotubes substantially aligned with a density greater than 104 nanotubes per square millimeter of substrate with a high separation density in the nanotube structure to provide a plurality of diffusion paths. In addition, the carbon nanotubes of this product 416 may have a distal open end of the substrate. Particularly useful are carbon nanotubes in the simple form of the present invention which have a diameter of 1 nm. These nanotubes form packets and are strong absorbers of hydrogen gas. The hydrogen can be introduced into the hollow core of the carbon nanotube by placing the product 416 in a high pressure chamber (not shown) and introducing hydrogen gas at relatively high pressures into the chamber to diffuse the hydrogen through the diffusion paths in carbon nanotubes. Also, hydrogen can diffuse into electropotently or electrochemically nanotubes.

In addition, the heated products 416 can be placed inside a hydrogen-rich atmosphere and allowed to cool, thereby dragging the hydrogen into the nanotubes. Because the lightweight carbon nanotubes of the present invention have relatively large cores and surface areas, large amounts of hydrogen can be stored within. The products of the present invention can also be used to form compounds with other different materials. Suitable different materials include metals, ceramics, glasses, polymers, graphite, and mixtures thereof. Such compounds are prepared by coating the products of the present invention with these different materials in solid particle form or in liquid form. A variety of polymers, including thermoplastics and resins, can be used to form compounds with the products of the present invention. Such polymers include, for example, polyamides, polyesters, polyethers, poly phenylenes, polysulphones, polyurethanes, or epoxy resins.

In another embodiment, the compound contains an inorganic material, for example, a ceramic material or a glass. For example, high temperature superconducting copper oxide ceramic materials, such as BiSrCaCuO (BSCCO), TlBaCaCuO (TBCCO), Bi2Sr2CaCu208 (Bi-2212), B i2Sr2Ca2Cu30? or (Bi-2223), Tl2Ba2Cu06 (Tl-2201), Tl2Ba2CaCu208 (Tl-2212), Tl2Ba2Ca2 Ca2Cu3O? 0 (Tl-2223), TlBa2CaCu207 (1212), TlBa2Ca2Cu3? 9 (Tl-1223), and any derived ceramic composition of these compositions, such as the partial replacement of IT with Bi, Pb, Bi, or Pb, Ba and Sr, and Ca with Y or Cr, are useful in the present invention. These ceramics are deposited in the products of the present invention by electronic arrangement of the magnetron, laser ablation, thermal vaporization, electron has evaporation, etc. to cover aligned carbon nanotubes, substantially perpendicular in the form of a superconducting material at high temperature. Due to the high degree of alignment of nanotubes, the interaction to fix the core to the excellent magnetic flux line can be obtained to increase the critical current densities (Jc) without destroying an unnecessary volume fraction of the superconductor. As discussed in Yang et al., "Nanorod-Superconductor Composites: A Pathway to Materials with High Critical Current Densities," Science. 273: 1836-1840 (1996), incorporated herein by reference, the large-scale applications of superconducting high temperature copper oxide ("HTSC") materials listed above require high Jc at temperatures near the boiling point of liquid nitrogen at be used technologically. Insert columnar defects in HTSC materials, the high Jc can be maintained at high temperatures when subjected to an electric current. Columnar defects can be executed by coating products of the present invention with HTSC materials. Accordingly, a high temperature superconductor comprises a product having a substantially non-electrically conductive substrate and either (1) a plurality of carbon nanotubes substantially aligned with a density greater than 104 nanotubes per square millimeter of substrate.; (2) a plurality of carbon nanotubes substantially aligned with a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an outer surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outward from an external surface of the substrate, a high temperature copper oxide superconducting material blended with the product, and at least two connectable separated space terminals. to an electrical circuit, by means of which the product and the mixed high temperature copper oxide superconducting material are subjected to an electric current. In yet another embodiment, the compound includes a metal. Suitable metals include aluminum, magnesium, lead, zinc, copper, tungsten, titanium, niobium, hafnium, vanadium, and alloys thereof. Referring to Figure 25 and generally to Figures 1-5B and 7-19, an electromagnetic interference shield (EMI) 500 is formed from a product of the present invention comprising a substrate either (1) a plurality of nanotubes of carbon substantially aligned with a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of carbon nanotubes substantially aligned with a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an outer surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outward from an outer surface of the substrate and a different material mixed with the product. The different material comprises a polymer, graphite, or a combination thereof. Such polymers are thermoplastics and resins and may include, for example, polyamides, polyesters, polyethers, polyphenylene, polyoles, polyurethanes, or epoxy resins. The electromagnetic interference shield 500 is operationally positioned with respect to either an electromagnetic source 502 or an electronic component 504. The composite can be used as an EMI protective material in the construction of gasket or gasket, housing of electronic components, including components within computers, conduction cables, and protection parts, EMI emission sources 502, and other applications known in the art. Depending on the substrate selected by the product, such as an EMI 500 protector is particularly useful in high temperature environments. In a process for the protection of an electronic component 504 against the EMI produced by the source of electromagnetic radiation 502, the EMI protector 500 of the present invention is interposed between the electronic device 504 and the source of electromagnetic radiation 502. The interference of the device 504 by the radiation source 502 is therefore reduced or substantially eliminated. An electronic component 504 protected for the EMI resistance generated by the electromagnetic source 502 has an electronic component 504 and an EMI protector 500 of the present invention operatively positioned with respect to the component 504. A source of protected electromagnetic emission 502 has a source 502 that emits EMI and an EMI protector 500 of the present invention operatively positioned with respect to the source 502. Yet, the products of the present invention can also be used to form a microelectrode 600, as shown in Figure 26 and discussed in Stulik et al., "Microelectrodes: Definition, Characterization and Hints for Their Use," IUPAC Commission, 5: Document No. 550/61/97 (1999), incorporated herein reference. The microelectrode 600 comprises a product having a non-electrically conductive substrate 602 and either (1) a plurality of carbon nanotubes 604 substantially aligned with a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of carbon nanotubes 604 substantially aligned with a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes 604, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes 604 originating and extending outwardly from an external surface of the substrate 602; or (5) one or more freestanding carbon nanotubes 604 that originate and extend outwardly from an outer surface 606 of the substrate 602 and at least one operable electrically conductive microfiber 608 connected to at least one carbon nanotube 604 of the product, in wherein at least one carbon nanotube 604 is operable and electrically connectable to an electrical circuit. Particularly well-placed for use as an electrode or electrode formation are carbon nanotubes having open ends, as shown in Figure 13. Carbon nanotubes are seeded onto a non-electrically conductive substrate, such as glass, quartz, or a ceramic. Carbon nanotubes are operably and electrically connectable to an electrical circuit with electrically conductive microfibers, such as platinum or carbon microfibers, attached to the nanotubes.

EXAMPLES Example 1 The single-crystal Ni substrates and polyclinic talc finish were placed in a chemical vapor deposition (CVD) chamber, and the pressure was reduced to < 6 x 10 ~ 6 Torr. Acetylene gas (purity 99.99%) and ammonia gas (purity 99.99%) were introduced into the chamber at a total flow rate of 120-200 standard cm3 per minute (sccm) and at a sustained operating pressure of 1-20. Torr under the conditions listed in Table 1. After the stabilization of the operating pressure, a spiral of tungsten filament activated by a DC source (about 0-500 V DC, 3 A power supply, Advanced Energy MDX 1.5K - induced by magnetron) and a plasma generator were energized to generate heat and plasma at a temperature below 666 ° C to induce the growth of the carbon nanotube. Samples of the carbon nanotubes were examined by scanning electron microscopy (SEM, Hitachi S-4000) to measure the lengths, diameters, location distributions, alignments, density and uniformity of the tubes. High resolution electron transmission (TEM) microscopy was used to determine the microstructure of the individual tubes. In addition, the samples were also examined by x-ray diffraction, Raman spectroscopy, and x-ray photoemission spectroscopy to study the structure, crystallinity, composition, and central core and tube wall structures.

Table 1. Growth conditions for the nanotubes shown in Figures 1 (A), 1 (B), 2, and 3.

C2H2 / NH3 Current of Plasma Intensity Time of (sccm / sccm) Filament (amperaj e / vc iltaje / atts) Growth (minutes) (A): for Figures 1 (A) and KB): 20/100 9 0. 09/460/50 90 (B): For Figure 2: 80/160 9 0.2 / 640/140 25 (C): For Figure 3: 40/80 6 0.3 / 700/220 20 Figure IA is a scanned image of a SEM micrograph showing the growth alignment of carbon nanotubes over nickel pol i cr i s such under the conditions described in Table 1 (A). As noted, the carbon nanotubes are oriented perpendicular to the surface of the substrate and are completely uniform in height. Carbon nanotubes do not grow well along the boundaries of the nickel grain, shown by the two empty runs that run from the top right and from the top left to the bottom. This is probably due to the fact that grain boundaries do not have enough of nickel available as a catalyst. Figure IB is a larger image of an area within a single nickel grain. Here, the uniformity of the nanotube distribution within this grain is reasonably good. Although there is a wide distribution of carbon nanotube diameters ranging from 60-500 nm, uniformity in both diameter and distribution of locations can be controlled via growth conditions. Here, the density of the carbon nanotube is approximately 106 nano tubes / mm2. Figure 2 is a scanned image of a SEM micrograph showing the growth of carbon nanotubes over nickel pol icies at high plasma density under the conditions listed in Table 1 (B). Most of the nanotube diameters are smaller (~ 250 nm), and either the distribution is narrower, ranging from 200 to 300 nm. With the increased plasma intensity, the density is increased to 4 x 106 nanotube / mm2, approximately 4 times more than that shown in Figure 1. The increase in plasma intensity apparently reduces the particle size of catalytic nickel, which it leads to both the thinner carbon nanotubes and the uniformity of the improved nanotube. Figure 3 is a scanned image of a SEM micrograph showing the growth of carbon nanotubes under the conditions listed in Table 1 (C). These carbon nanotubes were synthesized at a higher plasma intensity than that used by the carbon nanotubes of Figure 2. To keep the substrate at low temperature, the filament current is reduced from 9 to 6 amps. As shown in Figure 3, the carbon nanotubes are at least 10 μm long, and the diameters are <100 nm. By increasing the intensity of the plasma, two structural changes are easily observed. First, there is a substantial decrease in average tube diameters from ~ 250 nm, as shown in Figure 2, to ~ 100 nm, as shown in Figure 3. Second, the tube lengths increase dramatically. This high rate of growth is very attractive for large-scale potential production of carbon nanotubes with long lengths. However, when the diameters are < 20 nm, the tubes are less straight than those with diameters of > 50nm. The analysis of high-resolution electron transmission (TEM) microscopy of carbon nanotubes showed these film structures to be truly carbon nanotubes, as opposed to structures similar to carbon fiber. Samples with growth of carbon nanotubes at several microns in length were removed by scraping a nickel substrate directly on a copper TEM grid by analysis. Figure 4 shows a typical image obtained by these carbon nanotubes. The disorder is completely due to the accidental process of the nanotube collection on the TEM grid. The black spot at the end of each structure is a layer of a small ball of nickel, catalyst layer material in the current example. The image is typical of those reported elsewhere that demonstrate a carbon nanotube structure. However, the insertion to Figure 4, a high resolution image of a portion of a typical carbon nanotube structure, is more convincing. The width of this tube is ~ 30 nm and represents a highly defective multi-fortified structure with a hollow core. The diameter of the core is approximately 20 nm and the thickness of the wall is approximately 5-10 nm. The peripheries on each side of the tube identify the individual cylindrical graphitic layers. This particular carbon nanotube is a structure with approximately 15 graphitized carbon walls. Both the angular background in the structure and the appearance of the carbon walls that run through the diameter of the nanotube demonstrate the significant structural defects of the twist of the nanotube structure. As can be seen in structural defects, non-continuous walls intersect one another. On an atomic scale, the active surface creates cited defects for permeability through the structure of the nanotube. The lack of peripheries inside the nanotube, as well as the lighter contrast when compared to the walls of the nanotube, indicates that the core of the structure is hollow.

E jmplo 2 Substrate Preparation The display glass having a deformation point temperature of 666 ° C was cut into 10 x 5 mm pieces and cleaned in acetone by ultra sonication. The clean pieces were mounted on the surface of a rugged stainless steel heater, and the complete assembly was placed in a magnetron deposition chamber. The camera was operated below 8 x 'Torr before argon gas was introduced into the chamber to maintain an operating pressure of 20-60 mTorr. A layer of nickel catalyst of 15 to 60 nm thickness was deposited on the glass substrates by deposition of the magnetron for about 1.5 to 6 minutes. During the deposition, the substrates were heated or maintained at room temperature. The substrates with catalyst layer were placed in a CVD chamber, which was operated below 6 x 10"6 Torr.After the chamber pressure reached 6 x 10" d Torr, acetylene and ammonia gases were introduced into the chamber. the chamber to maintain an operating pressure of 1-20 Torr during the growth of the carbon nanotube. The total flow velocity of acetylene and ammonia gases was 120-200 sccm with a volume ratio of acetylene to ammonia ranging from 1: 2 to 1:10. After the operating pressure stabilized, the energy to the spiral of the tungsten filament y. The plasma generator, as described in Example 1, was energized to generate heat and plasma at a temperature below 666 ° C to induce growth of the carbon nanotube under the conditions listed in Table 2. Samples of the nanotube of carbon were examined as the manner described in Example 1. In particular, electron scanning microscopy was used to investigate the effect of various growth conditions on the growth morphology of carbon nanotubes on the nickel-coated display glass . As described in Table 2 (A), NH3 was introduced during the first 5 minutes without the introduction of C2H2. During this time, the catalyst layer was plasma etched by etching to reduce its thickness to less than 40 nm. After these additional 5 minutes, C2H2 was introduced. Immediately, a color change occurred as a result of the growth of carbon nanotubes. The period of continuous growth only 10 minutes. Referring to Figures 5A-B, to examine the orientation and alignment of the carbon nanotubes on the glass substrates, part of the area covered with carbon nanotube was detached (bottom left in Figure 5A) with a clamp to expose the glass substrate. During the peeling, another area was creased (bottom right in Figure 5A), and a long scratch was made over the open area detached (bottom left in Figure 5A). Under visual observations and SEM, the alignment of the carbon nanotubes across the entire surface was as uniform as in the upper part of Figure 5A. To estimate the length of the carbon nanotube, an SEM was taken at higher magnification along the detached cut (Figure 5B). The misalignment of the carbon nanotubes on the cut resulted from the detachment operation. From Figure 5B, it was estimated that the nanotubes were approximately 100 nm in diameter and 20 μm in length. Given the growth time of 10 minutes, the growth rate was calculated to be 120 μm / hour, approximately 5 times faster than the value reported with Li. As shown respectively in Figures 6A and 6B, the surfaces of the nickel layer after etching of the initial N2 or NH3 plasma are essentially the same. The conditions of etching by plasma are respectively listed in Table 2 (B) and 2 (C). For comparison, Figure 6C shows the smooth nickel surface subjected to electronic deposition. Although both the etching of NH3 plasma and the N2 harden the nickel surface, the hardening of the nickel surface is not responsible for the nucleation and growth of carbon nanotubes. Interestingly, when the sequence of gas introduction is reversed, which is when C2H2 is first introduced, 5 minutes later, followed by NH3, no growth of the carbon nanotubes is observed, only amorphous carbon is formed on the surface of nickel. The amorphous carbon layer is formed in the first 5 minutes and the C2H2 plasma covers the nickel surface to inhibit the catalytic role of nickel so that there is no growth of carbon nanotubes. Apparently, carbon nanotubes grow only when the catalyst gas (NH3) is first introduced followed by the carbon source gas (C2H2) or both the carbon source and the catalyst gases (C2H2 and NH3, respectively) are introduced. simultaneously. Therefore, it can be concluded that NH3 plays a crucial catalytic role together with the nickel layer to promote the growth of carbon nanotubes. The catalytic role of NH3 is further confirmed by the factor that there is no growth of carbon nanotube when the NH3 is replaced by N2 gas at temperatures below 700 ° C with other conditions unchanged. However, carbon nanotubes grow when NH3 is replaced by N2 at temperatures above 700 ° C using PE-HF-CVD.

To examine the effect of the thickness of the metal catalyst layer on the growth of the carbon nanotubes, C2H2 and NH were introduced at the same time under the conditions listed in Table 2 (D). Under these growth conditions, plasma etching did not occur, and the nickel layer maintained 40 nm in thickness. Referring to Figure 7A, the carbon nanotubes have an estimated location density of approximately 10 'tubes / mm2. The diameters of the carbon nanotubes (Figure 7A) are much longer than those in Figure 5B. From Figure 7B, it is estimated that the outer diameters of the carbon nanotubes vary from 180 to 350 nm, and more than the carbon nanotubes are approximately 250 nm in diameter. Although not shown, carbon nanotubes have been growing according to this method with diameters as long as 500 nm. This experiment clearly shows that the thickness of the catalyst layer is reduced, the diameters of the carbon nanotubes of the resulting growth are similarly reduced. As shown in Figure 7B, the catalytic role of nickel is also clearly indicated by the nickel layer on the end of each nanotube. Interestingly, a carbon nanotube, as indicated by an arrow in Figure 7B, does not have a nickel layer. Due to the absence of a layer on the identified nanotube, it can be concluded that the carbon nanotubes are empty with a very thin wall. In support of this conclusion, another carbon nanotube is visibly behind one that has no layer through its wall. Surprisingly, nanotubes have a central nucleus which is longer than the values reported in the literature. These long carbon nanotubes may be useful for applications such as gas storage, such as H2, and as microelectives. These experiments show a direct relationship between the thickness of the metallic catalyst layer and the diameters of the nanotube. That is, the thinnest is the nickel layer, the thinnest of the nanotubes. To further examine the effect of the thickness of the nickel layer on the growth of the carbon nanotube, a much thinner nickel layer of only 15 nm is used under the conditions listed in Table 2 (E) and 2 (F). In one experiment (Table 2 (F)), the thickness of the nickel layer is the etching of the plasma reduced by the introduction of NH first, and 20 minutes after the introduction of C2H2. In Figures 8A and 8B, respectively, the SEM micrographs of the growth of the carbon nanotubes under the conditions listed in Table 2 (E) and 2 (F) show the nanotube-dependent relationship to the thickness of the nickel layer . The typical diameter of the nanotubes in Figure 8A is only about 65 nm, compared to 240 nm in Figure 7B. Relatively speaking, the alignment in Figure 8A is not quite as good as in Figure 7B. A comparison of Figures 8A and 8B demonstrates that 20 minutes of plasma etching reduces the thickness of the nickel layer, which in turn results in even thinner carbon nanotubes with typical diameters of only about 20 nm. The comparison also shows that the alignment starts to deviate when the diameter of the nanotube is reduced to 20 nm. Carbon nanotubes have been produced according to this method having a diameter as small as 4 nm. Therefore, for applications that require substantial alignment of the nanotube, it is apparent that the diameters could be longer than 50 nm for carbon nanotubes having a length of 20 μm or longer. Again, high resolution TEM was used to determine the structures of the wall and the interior of the carbon nanotubes. The samples for a TEM of plan view were prepared as follows. Given the flexible nature of the nanotubes, the carbon nanotube film was penetrated with epoxy resin M-Bond 610 (M-Line Accessories) to provide mechanical rigidity. This resin has very low viscosity and the curing is dependent on the temperature / time. Hydrotetrafuran (diethylene oxide) makes up approximately 90% of the composition of M-Bond. The carbon nanotube film was immersed in acetone; then M-Bond epoxy was slowly added until a 1: 1 ratio was reached. The sample was cured at room temperature for 48 hours. Because the viscosity of the epoxy was very low then it was introduced into the sample, this easily impregnated the pores to completely mix the acetone. Standard mechanical thinning and ion grinding (low angle, low voltage and low current) were used to thin the sample to electron transparency. More of the substrates were removed mechanically, followed by ion grinding until the film was exposed. Then, both sides were ionically ground for 15 minutes. Figure 9A shows a cross-sectional view of a typical thinner carbon nanotube. This carbon nanotube is a multi-walled, central hollow tube with an external diameter of almost 30 nm. The peripheries on each side of the tube represent individual cylindrical graphite layers. This particular carbon nanotube has approximately 15 graphitized carbon walls. Both the angular curve in the structure and the appearance of the carbon walls running through the diameter of the nanotube show suggestive structural defects in the twisting of the nanotube structure. The lack of periphery within the tube, as well as the higher contrast compared to the walls of the nanotube indicates that the core of the structure is hollow. Additional evidence of the hollow core is shown in Figure 9B. This is a high resolution plan view TEM image of a single or single carbon nanotube structure. Here, the hollow nature of the nanotube, again represented by the lighter contrast of the inner core, is more easily observable. The disorder observed in the wall edges surrounding the hollow center is more likely caused by tornado-like defects or spinning along the entire length of the carbon nanotube as shown in Figure 9A. These high resolution TEM images show that the structures are multi-walled, hollow carbon nanotubes with defects that exist along the tube. The bending and bending defects of the carbon nanotubes of the thin carbon nanotubes shown in Figures 9A and 9B are consistent with the observation of "EM" in Figure 8B. In addition, there is an inverse relationship between CVD temperature and density defect. When the deposition temperature is reduced, the carbon nanotubes show an increase in the number of defects that occurs in the wall. On an atomic scale, these defects turn the wall of the discontinuous carbon nanotube. This results in an extremely high surface area, active and accessible due to the substantial alignment of and relatively large spacing between the carbon nanotubes. These discontinuities in the structure of the wall provide atomic disorder that results in an active surface through which diffusion of the atomic level can occur.

Table 2. Growth conditions for nanotubes shown in Figures 5, 6, 7, and 8.

C2H2 / NH3 / N2 Time Intensity Current (sccm / sccm) Filament (amperage, Plasma Growth A) (amperage / voltage / (minutes) watts (A): For Figures 5A and 5B 0/160/0 8.5 0.10 / 635/72 Followed by 80/160/0 8.5 0.13 / 670/95 10 (B): For Figure 6: 0/160/0 8.5 0. .09 / 740/66 3 (C): For Figure 6B: 0/0/296 8.5 0. .10 / 480/53 3 (D): For Figures 7A and 7B: 80/160/0 8.5 0, .20 / 700/150 25 (E): For Figure 8A: 40/160/0 7.2 0. .13 / 650/90 14 (F): For Figure 8B 20 0/160/0 8.0 0.10 / 480/52 s followed by 80/160/0 8.2 0.10 / 560 / 60 10 E j us 3 A glass substrate was prepared as in Example 2 with a nickel catalyst 10-40 nm thick having a smooth surface subjected to electron deposition, as shown in Figure 6C. The carbon nanotubes were cultured by PE-HF-CVD for about 10 minutes as in Examples 1 and 2, except that the volume ratio of acetylene and ammonia was 1: 2 to 1: 4. Figure 10 shows a large area growth of carbon nanotubes aligned substantially vertically. The length of the carbon nanotubes is up to 50 μm. The diameters are estimated to be in the range of 100-150 nm (See Figure 14).

E j empl o 4 Substrates silicone of 9.5 O-cm (100) mixed with p-type boron, single crystal, were prepared as in Example 2 with a layer of nickel catalyst 10-40 nm thick having a smooth surface subjected to electron deposition, as shown in the Figure 6C. The carbon nanotubes were cultured by PE-HF-CVD as in Examples 1 and 2, except that the volume ratio of acetylene to ammonia was 1: 2 to 1: 4. Figures 11 and 12 show carbon nanotubes which were cultured for 5 and 2 minutes, respectively. Referring to Figure 11, the alignment of the substantially perpendicular carbon nanotube is clearly shown. A layer of nickel, which acts as a catalyst to maintain growth, is also discernible at the top of each carbon nanotube. The growth of the carbon nanotube of the earliest stage is shown in Figure 12, since the growth was stopped at 2 minutes. The shorter nanotubes are approximately 0.1 μm.

Example 5 The carbon nanotubes were cultured as in Example 3. The catalyst metal layers were subsequently removed by etching by HN03 solution and electron iron deposition Ar. Figures 13 and 14 show the SEM image of the nanotubes after removal of the nickel layers by etching with HNO? and electronic deposition of Ar iron, respectively. The etching with the HN03 solution only took about a minute, and the removal of the nickel layers is complete. As shown in Figure 13, the ends of the carbon nanotubes open after etching. Morphologically, no damage was observed by the engraving with HN03. In Figure 14, all nanotubes are doubled by electron deposition of Ar iron, and the nickel layers were not completely removed. These techniques can be used to remove any of the metal or metal alloy layers. By removing the layers, several fillers (ie, hydrogen, lithium ions, bismuth, lead telluride, bismuth trithelide, a pharmacological agent, etc.) can be added to the nanotube core. Subsequently, if desired, the open ends can be sealed by the electrochemical deposition of a metal on the carbon nanotubes.

E j us 6 The carbon nanotubes were cultured as in Example 3, except that the substrates were placed in the CVD chamber at angles differing from the plasma generator. Although the carbon nanotubes grew substantially aligned with each other, the alignment was independent of the topography of the substrate surface. Figures 15 and 16 show the SEM image taken from one side and above on a sample site inclined at a certain angle during growth. It is observed that the alignment of carbon nanotubes is not perpendicular to the surface of the substrate, but better is angulated with respect to the substrate. The inclined direction is closely related to the direction of the electric field which generates the plasma. This technique can be used to cultivate carbon nanotubes aligned at any angle to the substrate, including nanotubes that are in a plane.

Example 7 A layer of nickel catalyst is deposited on a silicon substrate of 9.5 O-cm (100) mixed with p-type boron by lithography of electron beams and metal evaporation. A bilayer electron beam resistor (5% polymethylactyl 100% molecular weight) was coated with 2% molecular weight polymethyl methacrylate 950 which was configured with a JEOL J6400 SEM converted by lithography. The resistance was developed in a solution of methyl isobutyl ketone and isopropyl alcohol (3: 1). Subsequently, 150A of nickel was deposited by evaporation of bundles. A catalyst layer (ie, a large nickel pad of ~0.25 mm2, or one or more nanodots) remains after raising the strength / metal in acetone. The carbon nanotubes are cultured by PE-HF-CVD as in the process in Example 2, except that the growth was carried out at a pressure of 1-10 Torr with a mixture of acetylene to ammonia volume of 1: 4 to one. Total flow velocity of 200 sccm for approximately 5 minutes. Referring to Figures 17A-B, the scanned images of SEM micrographs show the growth of carbon nanotubes on the silicon substrate in the edge region of the nickel pad. As shown in Figure 17A, the absence of growth of nanotubes in the foreground demonstrates the selective growth on the nickel catalyst film and not on the silicon substrate. Figure 17B shows these nanotubes after they are mechanically broken using tweezers. Surprisingly, the tubes break somewhere along the tube and not at the interface between the nickel and silicon. This observation is different than that of the growth of nanotubes in nickel on glass, where the nanotubes are clearly broken at the interface of 1-glass, as shown in Figure 5A.

Example The nickel catalyst nanopoint configurations were deposited on a silicon substrate of 9.5 O-cm (100) mixed with p-type boron by electron beam lithography and metal evaporation as in Example 7. Carbon nanotubes were cultured by PE-HF-CVD as in the process in Example 7, except that the growth or culture temperature was between 300 ° C and 666 ° C and only a simple, self-supporting carbon nanotube grew at each nickel nanopoint. Subsequently, the carbon samples were examined by SEM, TEM, XPS, etc., techniques as described above. Figure 18 is a series of SEM micrographs illustrating the growth of simple multi-walled carbon nanotube obelisks on respective nickel catalyst nanopoints. The catalyst nanodots are shown in arrays of ~ 100 nm of catalyst nanodots. The site and spacing are controlled precisely. Figures 18A, 18C, and 18F are perspective views of the nanotubes, and Figures 18B and 18D are top views of the nanotubes. Figures 18A and 18B demonstrate the selective growth of the nanotubes over several repeated array configurations. The nanotubes accurately reflect the spacing and periodicity of the catalyzed catalyst nanopoints 1 and topographically. Figures 18C and 18D reflect upper magnification and show the repeated array configuration where the nanotubes are spaced either 2 μm away (left portion of the array) or 1 μm away (right portion of the array). The tapered, sharp ends of the nanotubes shown in Figures 18E, 18F and 19 are unique for carbon nanotubes grown on nanodots under the present conditions. Notably, such nanotubes do not have a layer of the catalyst material. In Figure 18F, the nanodots are spaced 5 μm away. The non-uniformity of height (0.1 to 5 μm) is evidently not related to spatial position. Rather, it is believed to be due to the lithography of non-uniform electron beams and evaporation of electron beams from the catalyst nanodots on the substrate. With precise control of electron beam lithography, all carbon nanotubes should be substantially uniform in height. The length of nanotubes is dependent on the growth time and thickness of the nanodots, although the diameter of the nanotube depends on the diameter of the nanotubes. It can be seen that although the heights vary, the diameters are generally uniform at 150 nm. Using the placement of controlled nanopoints on the substrate, single or multiple carbon nanotubes with controlled site density can be achieved. For example, the direct growth of a single or single carbon nanotube over the probe end of the scanned or scanned tunneling microscope (STM), the atomic force microscope (for its acronym) can be achieved. in English, AFM). The well-defined spacing of multiple carbon nanotubes with multi-electron beam lithography can improve the configuration ability by 104-106 times. Although the invention has been described in detail for the purposes of illustration, it is understood that such details are solely for this purpose, and variations may be made here by those skilled in the art, without departing from the spirit and scope of the invention which It is defined by the following claims. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property.

Claims (86)

1. A product comprising a plurality of substantially aligned carbon nanotubes attached to a substrate at a density greater than 104 nanotubes per square millimeter of substrate.

2. A product according to claim 1, characterized in that the carbon nanotubes extend out from and substantially perpendicular to the substrate.

3. A product according to claim 1, characterized in that the carbon nanotubes extend outwards and at an angle not perpendicular to the substrate.

4. A product according to claim 1, characterized in that the carbon nanotubes extend substantially parallel to the substrate.

5. A product according to claim 1, characterized in that the nanotubes have a diameter between 4 to 500 nanometers.

6. A product according to claim 1, characterized in that the nanotubes have a diameter of at least 50 nanometers.

7. A product according to claim 1, characterized in that the substrate has a temperature of deformation point or melting point up to 3000 ° C.

8. A product according to claim 1, characterized in that the substrate has a deformation point or melting point temperature of at least about 300 ° C.

9. A product according to claim 1, characterized in that the substrate comprises glass, silica, quartz, silicon, iron, cobalt, nickel, an alloy of iron, cobalt, or nickel, platinum, a ceramic or a combination thereof.

10. A product according to claim 9, characterized in that the substrate is a glass plate.

11. A product according to claim 9, characterized in that the substrate is a silicon plate.

12. A product according to claim 1, characterized in that substantially all carbon nanotubes have a layer remote from the substrate comprising a metal or a metal alloy.

13. A product according to claim 12, characterized in that the layer is iron, cobalt, nickel or an alloy of iron, cobalt or nickel.

14. A product according to claim 13, characterized in that the layer is nickel.

15. A product according to claim 1, characterized in that it also comprises a filling inside the carbon nanotubes.

16. A product according to claim 1, characterized in that all the carbon nanotubes have an open end.

17. A product according to claim 16, characterized in that it also comprises a filling inside the carbon nanotubes.

18. A product according to claim 17, characterized in that the filler is hydrogen, lithium ions, bismuth, lead telluride, or bismuth tritelide.

19. A product according to claim 17, characterized in that the filling is a pharmacological agent.

20. A product according to claim 17, characterized in that the filling is enclosed within the carbon nanotubes.

21. A product comprising a plurality of substantially aligned carbon nanotubes attached to a substrate at a density no greater than 102 nanotubes per square millimeter of substrate.

22. A product according to claim 21, characterized in that the carbon nanotubes extend outwards and substantially perpendicular to the substrate.

23. A product according to claim 21, characterized in that the carbon nanotubes extend outwardly and at an angle not perpendicular to the substrate.

24. A product according to claim 21, characterized in that the carbon nanotubes extend substantially parallel to the substrate.

25. A product according to claim 21, characterized in that the nanotubes have a diameter between 4 to 500 nanometers.

26. A product according to claim 21, characterized in that the nanotubes have a diameter of at least about 50 nanometers.

27. A product according to claim 21, characterized in that the substrate has a temperature of deformation point or melting point of up to 3000 ° C.

28. A product according to claim 21, characterized in that the substrate has a deformation point or melting point temperature of at least about 300 ° C.

29. A product according to claim 21, characterized in that the substrate comprises glass, silica, quartz, silicon, iron, cobalt, nickel, an alloy of iron, cobalt, or nickel, platinum, a ceramic or a combination thereof.

30. A product according to claim 29, characterized in that the substrate is a glass plate.

31. A product according to claim 29, characterized in that the substrate is a silicon plate.

32. A product according to claim 21, characterized in that it also comprises the filling inside the carbon nanotubes.

33. A product according to claim 21, characterized in that substantially all of the carbon nanotubes have an open end.

34. A product according to claim 33, characterized in that it also comprises a filling inside the carbon nanotubes

35. A product according to claim 34, characterized in that the filler is hydrogen, lithium ions, bismuth, lead tellurium, bismuth trithelide, or a pharmacological agent.

36. A product according to claim 34, characterized in that the filling is enclosed within the carbon nanotubes.

37. A product characterized in that it comprises a substrate having a deformation point temperature or melting point between about 300 ° C 700 ° C one or more carbon nanotubes.

38. A product characterized in that it comprises a substrate having an external surface and a plurality of substantially aligned carbon nanotubes that originate and extend outwardly from the outer surface.

39. A product characterized in that it comprises a substrate having an external surface and one or more freestanding carbon nanotubes that originate and extend from the external surface.

40. A method of forming a product with one or more carbon nanotubes on a substrate comprising: providing a substrate in a reduced pressure environment containing a carbon source gas and a catalyst gas and exposing the substrate to a plasma under conditions effective to cause the formation and growth of one or more carbon nanotubes on the substrate.

41. A method according to claim 40, characterized in that the environment of reduced pressure has a pressure between approximately 0.1 to 100 Torr.

42. A method according to claim 41, characterized in that the environment of reduced pressure has a pressure between approximately 1 to approximately 20 Torr.

43. A method according to claim 40, characterized in that the product has a temperature of deformation point or melting point between 300 ° C 3000 ° C.

44. A method according to claim 40, characterized in that the substrate comprises glass, silica, quartz, mesoporous silicon, silicon, iron, cobalt, nickel, an alloy of iron, cobalt or nickel, platinum, a ceramic, or a combination thereof. my smo s

45. A method according to claim 44, characterized in that the substrate is a glass plate.

46. A method according to claim 44, characterized in that the substrate is a silicon plate.

47. A method according to claim 40, characterized in that the carbon source gas is a hydrogen compound and branched, linear or saturated cyclic carbon having up to six carbon atoms.

48. A method according to claim 47, characterized in that the carbon source gas is acetylene, ethylene or benzene.

49. A method according to claim 40, characterized in that the catalyst gas is ammonia or nitrogen.

50. A method according to claim 40, characterized in that the volume ratio of gas from carbon source to catalyst gas varies from 1: 2 to about 1:10.

51. A method according to claim 40, characterized in that the substrate is exposed to the plasma at a temperature below 700 ° C.

52. A method according to claim 40, characterized in that the substrate is exposed to the plasma at a temperature below about 300 ° C.

53. A method according to claim 40, characterized in that the substrate is exposed to the plasma at a temperature between 300 ° C to 3000 ° C.

54. A method according to claim 40, characterized in that it further comprises: placing a catalyst film on the substrate by the electronic deposition of radiofrequency magnetron prior to providing the substrate in a reduced pressure environment containing a carbon source gas and a catalyst gas.

55. A method according to claim 40, characterized in that the substrate has a catalyst film placed therein.

56. A method according to claim 55, characterized in that the film has a thickness of at least about 15 nanometers.

57. A method according to claim 55, characterized in that the film is nickel, iron, cobalt, or an alloy of nickel, iron or cobalt.

58. A method according to claim 57, characterized in that the film is nickel.

59. A method according to claim 55, characterized in that it further comprises: varying the diameter of carbon nanotubes in direct proportion to the thickness of the film.

60. A method according to claim 40, characterized in that it further comprises: placing a nanopunto of catalyst on the substrate by evaporation of electron beams, thermal evaporation, or electronic deposition of magnetrons prior to providing the substrate in a reduced pressure environment containing carbon source gas and a catched gas r.

61. A method according to claim 60, characterized in that each nanopunto forms a carbon nanotube.

62. A method according to claim 40, characterized in that the substrate has at least one nanopoint of catalyst placed therein.

63. A method according to claim 62, characterized in that each nanopunto forms a carbon nanotube.

64. A method according to claim 62, characterized in that at least one nanopoint is nickel, iron, cobalt or an alloy of nickel, iron, or cobalt.

65. A method according to claim 64, characterized in that at least one nanopoint comprises nickel.

66. A method according to claim 40, characterized in that it further comprises: varying the diameter of the carbon nanotube in inverse proportion to the intensity of the plasma.

67. A method according to claim 40, characterized in that it further comprises: varying the length of the carbon nanotube in direct proportion to the plasma intensity.

68. A method according to claim 40, characterized in that one or more carbon nanotubes have a layer, and further comprises: removing the layer from one or more carbon nanotubes to form the open end on one or more carbon nanotubes.

69. A method according to claim 68, characterized in that the layer is removed by etching with HN03 solution.

70. A method according to claim 68, characterized in that the layer is removed by electron deposition of argon ions.

71. A method according to claim 68, characterized in that it also comprises: adding a filler in one or more carbon nanotubes after the removal of the layer.

72. A method according to claim 71, characterized in that it further comprises: enclosing the open ends of one or more carbon nanotubes after the addition of a filler to store the filler within one or more carbon nanotubes.

73. A method according to claim 72, characterized in that the open ends of one or more carbon nanotubes are enclosed by the electrochemical deposition or magnetron electronic deposition of a methanol on one or more carbon nanotubes.

74. A method according to claim 40, characterized in that one or more carbon nanotubes have a closed end and further comprises: exposing one or more carbon nanotubes to oxygen under effective conditions to remove the closed end.

75. A method according to claim 74, characterized in that it further comprises: adding a filler in one or more carbon nanotubes.

76. A method according to claim 74, characterized in that it further comprises: enclosing one or more carbon nanotubes after the addition of a filler to store the filler within one or more carbon nanotubes.

77. A method according to claim 76, characterized in that one or more carbon nanotubes are enclosed by electrochemical deposition or electronic magnetron deposition of a metal on one or more carbon nanotubes.

78. An emission display device by field effect characterized in that it comprises: a base plate having an arrangement emitting electrons placed therein and a phosphor coated plate spaced away from the base plate so that the electrons emitted from of this arrangement collide on the phosphor coating, wherein the base plate comprises a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a deformation point or melting point temperature between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes originating and extending outwardly from an external source of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate.

79. An electron emitter characterized in that it comprises: a source that generates electrons and a product having at least one carbon nanotube operably connected to the source that generates electrons to emit electrons from at least one carbon nanotube, wherein the product comprises a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of substrate; (3) one or more carbon nanotubes, wherein the product has a deformation point or melting point temperature between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate.

80. A scanning or electron scanning microscope characterized in that it comprises: a vacuum chamber capable of receiving a specimen; a source of electrons to produce electrons; a probe to emit and direct the electrons towards and explore the specimen operably placed inside the chamber of acío; a detector operably placed within the vacuum chamber to collect the radiation output from the specimen as a result of scanning by the probe to produce an output signal; and an exhibit screen operably connected to the detector to display an image of the specimen area scanned by the probe, wherein the probe comprises a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a deformation point or melting point temperature between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate.

81. A battery characterized in that it comprises: an anode; a cathode; an insulator placed between the anode and the cathode; and an electrolyte, wherein at least one of the anode and the cathode comprises a product having a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density not greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes originating and extending outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate.

82. An energy cell characterized in that it comprises: a housing; a gas diffusion anode positioned within the housing to form an anode side; a gas diffusion cathode positioned within the housing to form a side of the cathode; a matrix impregnated with electrolyte or ion exchange membrane placed between and in electrical contact with the anode and the cathode; an external circuit that electrically and operably connects the anode to the cathode; and a closed hydrogen storage unit operably connected to the anode side comprising a product having a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate, wherein substantially all of the carbon nanotubes have at least one diffusion path; and hydrogen gas placed inside the carbon nanotubes.

83. A compound characterized in that it comprises: a product comprising a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density not greater than 102 nanotubes per square millimeters of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outward from an external surface of the substrate and a different material in admixture with the product, wherein the different material is selected from the group consisting of metal, ceramic , glass, polymer, graphic, and mixtures thereof.

84. An elevated temperature superconductor characterized in that it comprises: a product having a substantially non-electrical conductive substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density not greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate, a high temperature copper oxide superconducting material in admixture with the product; and at least two terminals spaced apart electrically connected to the product mixture and the high temperature copper oxide superconducting material and which is coupled with an electrical circuit.

85. An electromagnetic interference field (EMI) characterized in that it comprises: a product comprising a substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or deformation point between about 300 ° C and 700 ° C; (4) a plurality of substantially aligned carbon nanotubes that originate and extend outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outward from an external surface of the substrate and a different material in admixture with the product, wherein the different material is a polymer, graphite, or a combination of the same, where the field of electromagnetic interference is operationally placed with respect to either an electromagnetic source or an electronic component.

86. A microelectrode characterized in that it comprises: a product comprising a substantially non-electrical conductive substrate and either (1) a plurality of substantially aligned carbon nanotubes of a density greater than 104 nanotubes per square millimeter of substrate; (2) a plurality of substantially aligned carbon nanotubes of a density no greater than 102 nanotubes per square millimeter of a substrate; (3) one or more carbon nanotubes, wherein the substrate has a melting point or boiling point between about 300 ° C and 700 ° C; (4) a plurality of sub-aligned carbon nanotubes that originate and extend outward from an external surface of the substrate; or (5) one or more freestanding carbon nanotubes that originate and extend outwardly from an external surface of the substrate and at least one electrically conductive microfiber operably connected to at least one carbon nanotube of the product, wherein at least one Carbon nanotube can be connected operably and electrically to an electrical circuit. SUMMARY OF THE INVENTION One or more highly oriented, multi-walled carbon nanotubes are grown on an external surface of a substrate initially placed with a catalyst film or catalyst nanopoint by hot vapor deposition of hot filament enhanced by plasma from a gas source. carbon and a catalyst gas at temperatures between 300 ° C and 3000 ° C. Carbon nanotubes vary from 4 to 500 nm in diameter and 0.1 to 50 μm in length depending on growth conditions. The density of the carbon nanotube can exceed 104 nano tubes / mm2. Acetylene is used as the carbon source gas, and ammonia is used as the catalyst gas. Plasma intensity, ratio of gas from carbon source to catalyst gas and its flow rates, the thickness of the catalyst film, and the deposition temperature of the chemical vapor affect the lengths, diameters, density, and uniformity of the nanotubes of carbon. The carbon nanotubes of the present invention are useful in electrochemical applications as well as in electron emission, structural compound, material storage, and microel ect applications.