US20020004136A1 - Carbon nanotubes on a substrate - Google Patents
Carbon nanotubes on a substrate Download PDFInfo
- Publication number
- US20020004136A1 US20020004136A1 US09/333,876 US33387699A US2002004136A1 US 20020004136 A1 US20020004136 A1 US 20020004136A1 US 33387699 A US33387699 A US 33387699A US 2002004136 A1 US2002004136 A1 US 2002004136A1
- Authority
- US
- United States
- Prior art keywords
- recited
- carbon nanotubes
- substrate
- nanotube
- array
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/08—Aligned nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S427/00—Coating processes
- Y10S427/102—Fullerene type base or coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
- Y10S977/843—Gas phase catalytic growth, i.e. chemical vapor deposition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
- Y10T428/12438—Composite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
Definitions
- the present invention relates generally to the synthesis of carbon nanotubes on substrates. More specifically, the invention relates to dense arrays of well-aligned carbon nanotubes filled with conductive filler synthesized on conductive substrates and a method for making these carbon nanotubes.
- Carbon nanotubes constitute a new class of materials with a broad range of potential applications. Their unique properties make carbon nanotubes ideal candidates for novel application in areas such as vacuum microelectronics, flat panel displays, scanning probes and sensors, field emission devices and nanoelectronics.
- carbon nanotubes can now be produced in high yield and with reasonable quality as reported by C. Journet et al., Nature 388, 756 (1997), using arc discharge, by A. Thess et al., Science 273, 483 (1996), using laser ablation, and by R. T. Baker, Carbon 27, 315 (1989), using thermal decomposition of hydrocarbons.
- Alignment of carbon nanotubes is particularly important for their use in applications such as flat panel displays.
- Ajayan et al., Science 265, 1212 (1994) report manufacturing a composite with carbon nanotubes randomly dispersed inside a polymer resin matrix and found that slicing the composite caused partial alignment of the nanotubes on the cut surface.
- De Heer et al., Science 268, 845 (1995) fabricated partially aligned nanotube films by drawing a nanotube suspension through a micropore filter.
- hollow carbon nanotubes have substantial utility, it is recognized that filling the hollow core of carbon nanotubes with materials having useful physical, chemical, and electronic properties significantly broadens the range of potential applications for carbon nanotubes.
- Early attempts to fill carbon nanotubes were based on electric arc or laser ablation methods using metal/carbon composites as reported for example by Zhang et all., Science 281, 973 (1998), or on capillary-force infiltration of open-ended nanotulbes as reported by Ugarte et al., Science 274, 1897 (1996).
- the present invention includes carbon nanotubes whose hollow cores are 100% filled with conductive filler.
- the carbon nanotubes are in uniform arrays on a conductive substrate and are well-aligned and can be densely packed.
- the uniformity of the carbon nanotube arrays is indicated by the uniform length and diameter of the carbon nanotubes, both which vary from nanotube to nanotube on a given array by no more than about 5%.
- the alignment of the carbon nanotubes is indicated by the perpendicular growth of the nanotubes from the substrates which is achieved in part by the simultaneous growth of the conductive filler within the hollow core of the nanotube and the densely packed growth of the nanotubes.
- the present invention provides a densely packed carbon nanotube growth where each nanotube is in contact with at least one nearest-neighbor nanotube.
- the substrate is a conductive substrate coated with a growth catalyst, and the conductive filler can be single crystals of carbide formed by a solid state reaction between the substrate material and the growth catalyst.
- the present invention further provides a method for making the filled carbon nanotubes on the conductive substrates.
- the method includes the steps of depositing a growth catalyst onto the conductive substrate as a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel to increase and maintain the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel. Additionally, varying the density and separation of the catalyst particles on the conductive substrate can be used to control the diameter of the nanotubes.
- H2/inert e.g. Ar
- FIG. 1 a is a photograph of a scanning electron microscopy micrograph illustrating the dense and well-aligned morphology of the carbon nanotube films.
- FIG. 1 b is a photograph of a scanning electron microscopy micrograph illustrating the structure of the carbon nanotubes.
- FIG. 1 c is a photograph of a scanning electron microscopy micrograph illustrating a tilted carbon nanotube revealing the structure of a nanowire enclosed within.
- FIG. 2 a is a photograph of a cross-sectional transmission electron microscopy illustrating the nature of the conductive fillers (nanowires) filling the core of carbon nanotubes.
- FIG. 2 b is an energy-dispersive x-ray spectra illustrating that the core of the conductive filler (nanowire) is comprised of both titanium and carbon.
- FIG. 2 c is a photograph of a high resolution transmission electron microscopy illustrating that the carbon walls are disordered graphite.
- the present invention is an array of a plurality of carbon nanotubes where each nanotube is attached to a substrate and extends from the substrate and has a closed outer wall defining a hollow core that is simultaneously filled more than 10% with a conductive filler while the carbon nanotube grows.
- the present invention further provides a method for making this array of carbon nanotubes which includes the steps of depositing a growth catalyst onto the substrate to form a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel and increasing the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel.
- H2/inert e.g. Ar
- the arrays of the carbon nanotubes filled with conductive filler are fabricated by first depositing a thin layer of growth catalyst onto a substrate.
- Depositing the growth catalyst is preferably by electron beam evaporation, and preferably results in a thin layer on the substrate which is about 1 to 30 nanometers in thickness.
- the substrate is an electrically conductive substrate, preferably made of metals including but not limited to transition elements appearing in groups IIIB, IVB, VIB, VIIB, VIII, and IB of the periodic table.
- Preferred metals are titanium, vanadium, tantalum, and combinations thereof. Non-metals such as carbides may also be used for the substrate, for example, titanium carbide.
- the growth catalyst is preferably iron, but may also be iron oxide and combinations thereof.
- the vessel which contains the prepared substrate is evacuated to a first pressure below 2 torr.
- the vessel is preferably a quartz reactor placed within a tube furnace.
- the pressure within the vessel is then increased to a second pressure within the range from about 200 torr to about 400 torr by flowing H2/inert (e.g. Ar) gas within the vessel.
- H2/inert e.g. Ar
- the prepared substrate is heated using the tube furnace. Once the prepared substrate temperature reaches the growth temperature, which can range from about 650° C. to about 800° C., but which is preferably from about 700° C.
- the H 2 /Ar flow is stopped and ethylene gas, preferably but not necessarily with a purity of about 99.5%, is introduced into the reactor.
- ethylene gas preferably but not necessarily with a purity of about 99.5%
- the heat treatment of the prepared substrate can be controlled to vary the density and separation of catalyst particles on the prepared substrate.
- a higher heat results in more coalescing of the catalyst particles, and thus, fewer and larger catalyst sites, which results in separation distances between these sites on the substrate.
- the density of the catalyst sites controls the diameter of the carbon nanotubes with a higher density resulting in a greater diameter carbon nanotube.
- the ethylene gas flows, it decomposes as a carbon source and diffuses into the catalyst particles causing precipitation and growth of the carbon nanotubes.
- the substrate material diffuses into the catalyst particles resulting in the growth of a carbide core (conductive filler) within the hollow carbon nanotubes.
- the carbide core within the carbon nanotubes is a conductive filler preferably made up of carbon and titanium.
- the conductive filler may also be made up of carbon and whichever metal makes up the conductive substrate, which includes but is not limited to transition elements appearing in groups IIIB, IVB, VIB, VIIB, VIII, and IB of the periodic table.
- Preferred metals are titanium, vanadium, tantalum, and combinations thereof.
- the hollow core of each carbon nanotube is filled with the conductive filler to a point which is greater than 10% full, but which is preferably greater than 50% full, and which is more preferably greater than 75% full, and which is most preferably about 100% full, where “about 100%” means 100%, plus or minus 5%.
- the carbon nanotubes have lengths ranging from about 1 to 2 ⁇ m, varying no more than about 5%, which provides uniform lengths.
- the carbon nanotubes also have uniform diameters such that their diameters vary no more than about 5%.
- the outside nanotube diameter ranges from less than 40 to about 400 nm and the inside nanotube diameter ranges from about 10 to about 100 nm.
- the diameters of the carbon nanotubes and filled cores can be controlled by varying the thickness of the catalyst (iron) layer. In general, the thicker the iron catalyst layer, the bigger the tube diameter. However, when the tube diameter is less than 40 nm, the carbon nanotubes are curved and only partially filled.
- a number of substrates were selected to investigate their effects on the formation of the filled carbon nanotubes.
- the formation of the filled nanotubes depends on the solubility of the iron (the catalyst) in the substrate and the free energy of formation for the respective carbide phase.
- the substrates selected included tantalum, silicon, and molybdenum. All of these materials can form stable carbides.
- Carbon nanotubes were deposited on the substrates under the same growth conditions used for growth of carbon nanotubes on titanium substrates. While dense arrays of filled carbon nanotubes were observed on tantalum substrates similar to those shown in FIG. 1 a , only curved hollow carbon nanotubes were formed on silicon substrates. No carbon nanotubes were observed on molybdenum substrates.
- X-ray photoelectron spectrometry and backscattering electron SEM indicated formation of Fe—Mo solid solutions in the surface region of the substrates.
- the high solubility of Fe in Mo depleted the catalytic material required to grow the carbon nanotubes.
- the driving force to form SiC is much lower than that for the formation of either TiC or TaC.
- the free energy of formation of these carbides is on the order of ⁇ 43 kcal/mol for TiC, ⁇ 35 kcal/mol for TaC, and ⁇ 15 kcal/mol for SiC.
- carbon nanotubes are formed on silicon, the growth rate of SiC is very low compared to that of TiC or TaC, resulting in hollow carbon nanotubes. These tubes tend to be tilted or curved.
- FIG. 1 a reveals the dense, well-aligned morphology of the carbon nanotube films.
- the SEM images were recorded using 70% secondary electron signals and 30% back scattering electron signals. The intensity is therefore proportional to the atomic number of the elements that comprise the material.
- a magnified SEM image (FIG. 1 b ) shows that the structure of the carbon nanotubes of the present invention is different from that of oriented carbon nanotubes previously reported.
- the carbon tubes are densely packed, rather than well separated as with prior reported carbon nanotubes.
- the tube tips as shown in FIG. 's 1 a , 1 b , & 1 c appear brighter at the center of the carbon nanotubes, indicating that the cores of the carbon nanotubes are filled with a material having elements of higher atomic number than carbon.
- FIG. 1 a Most of the carbon nanotubes filled with conductive filler of the present invention in FIG. 1 a have similar length and are approximately perpendicular to the substrate surface, although in a few cases the conductive filler is tilted and extended above the film surface.
- a SEM image (FIG. 1 c ) of a tilted nanotube reveals a structure of conductive filler enclosed by carbon. The filled material has a large head near the tube tip, and its diameter is about one quarter of the carbon nanotube diameter.
- Further evidence of filled cores and carbon caps is provided by the cross-sectional TEM image in FIG. 2 a and energy-dispersive xray (EDX) spectra illustrated in FIG. 2 b .
- FIG. 2 a shows that individual conductive filler grows continuously from the bottom to the top of the films.
- the filled nature of the carbon nanotubes can be clearly seen by the distinct contrast between the filled core and carbon wall.
- the cross-sectional TEM image in FIG. 2 a reveals that the cores have a large head near the tube tip, in agreement with the SEM image (FIG. 1 c ).
- the core diameter in the cross-sectional TEM image in FIG. 2 a appears slightly smaller than that observed in the SEM image (FIG. 1 c ), presumably due to the off-center cut of the TEM specimen.
- EDX analysis revealed that the walls and caps of the conductive fillers are carbon.
- a high-resolution TEM image (FIG. 2 c ) reveals that the carbon walls are disordered graphite.
- EDX analysis of the carbon nanotube and conductive filler of the present invention also indicates that the core of the conductive filler is comprised of titanium and carbon except for the region near the substrate where iron was found.
- Electron diffraction patterns obtained from the cores reveal that the cores are cubic TiC.
- the convergent beam electron diffraction pattern (inset in FIG. 2 a ) recorded along the ⁇ 001> zone axis parallel to the electron beam exhibits a lattice spacing ( ⁇ 0.43 nm) and four-fold symmetry corresponding to the (100) planes of cubic TiC.
- the electron diffraction patterns reveal that the TiC cores are single crystals.
Abstract
Description
- [0001] This invention was made with Government support under Contract DE-AC0676RLO1830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
- The present invention relates generally to the synthesis of carbon nanotubes on substrates. More specifically, the invention relates to dense arrays of well-aligned carbon nanotubes filled with conductive filler synthesized on conductive substrates and a method for making these carbon nanotubes.
- Carbon nanotubes constitute a new class of materials with a broad range of potential applications. Their unique properties make carbon nanotubes ideal candidates for novel application in areas such as vacuum microelectronics, flat panel displays, scanning probes and sensors, field emission devices and nanoelectronics.
- A wide range of techniques has been used to prepare carbon nanotubes. For example, carbon nanotubes can now be produced in high yield and with reasonable quality as reported by C. Journet et al.,Nature 388, 756 (1997), using arc discharge, by A. Thess et al., Science 273, 483 (1996), using laser ablation, and by R. T. Baker, Carbon 27, 315 (1989), using thermal decomposition of hydrocarbons.
- Alignment of carbon nanotubes is particularly important for their use in applications such as flat panel displays. Ajayan et al.,Science 265, 1212 (1994) report manufacturing a composite with carbon nanotubes randomly dispersed inside a polymer resin matrix and found that slicing the composite caused partial alignment of the nanotubes on the cut surface. De Heer et al., Science 268, 845 (1995) fabricated partially aligned nanotube films by drawing a nanotube suspension through a micropore filter.
- More recently, well-aligned carbon nanotube arrays have been synthesized on solid substrates. W. Z. Li et al., Science274,1701 (1996), report well-aligned carbon nanotube arrays synthesized by thermal decomposition of acetylene gas in nitrogen on porous silica containing iron nanoparticles, and Z. F. Ren et al., Science 282, 1105 (1998), report well-aligned carbon nanotube arrays synthesized by hot-filament plasma-enhanced thermal decomposition of acetylene gas on nickel-coated glass. All of these preparations however, result in isolated carbon nanotubes on substrates where all the nanotubes are separated by distances on the order of 100 nanometers within the arrays. Disadvantages of these separations between the carbon nanotubes include decreased nanotube capacity on the substrate and a decreased ability to maintain alignment as the nanotubes grow longer.
- Although hollow carbon nanotubes have substantial utility, it is recognized that filling the hollow core of carbon nanotubes with materials having useful physical, chemical, and electronic properties significantly broadens the range of potential applications for carbon nanotubes. Early attempts to fill carbon nanotubes were based on electric arc or laser ablation methods using metal/carbon composites as reported for example by Zhang et all.,Science 281, 973 (1998), or on capillary-force infiltration of open-ended nanotulbes as reported by Ugarte et al., Science 274, 1897 (1996). In addition, Dia et al., Nature 375, 769 (1995), reported an attempt to fill carbon nanotubes resulting in the reaction of the carbon nanotubes with titanium oxide (TiO) which converted all the nanotubes into titanium carbide (TiC) nanorods. In these and other prior experiments the carbon nanotubes were found to be only partially filled to a level of approximately 10%. The disadvantage of having carbon nanotubes that can only be partially filled is a decrease in the benefit sought to be gained through the useful properties of the materials filling the nanotube cores.
- In view of the current and potential applications for carbon nanotubes, there remains a need in carbon nanotube technology for a method of synthesizing dense arrays of well-aligned carbon nanotubes on conductive substrates where the nanotubes are simultaneously and completely filled with conductive materials.
- The present invention includes carbon nanotubes whose hollow cores are 100% filled with conductive filler. The carbon nanotubes are in uniform arrays on a conductive substrate and are well-aligned and can be densely packed. The uniformity of the carbon nanotube arrays is indicated by the uniform length and diameter of the carbon nanotubes, both which vary from nanotube to nanotube on a given array by no more than about 5%. The alignment of the carbon nanotubes is indicated by the perpendicular growth of the nanotubes from the substrates which is achieved in part by the simultaneous growth of the conductive filler within the hollow core of the nanotube and the densely packed growth of the nanotubes. The present invention provides a densely packed carbon nanotube growth where each nanotube is in contact with at least one nearest-neighbor nanotube. The substrate is a conductive substrate coated with a growth catalyst, and the conductive filler can be single crystals of carbide formed by a solid state reaction between the substrate material and the growth catalyst.
- The present invention further provides a method for making the filled carbon nanotubes on the conductive substrates. The method includes the steps of depositing a growth catalyst onto the conductive substrate as a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel to increase and maintain the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel. Additionally, varying the density and separation of the catalyst particles on the conductive substrate can be used to control the diameter of the nanotubes.
- It is an object of the present invention to provide a method for the synthesis of dense arrays of well-aligned carbon nanotubes on conductive substrates prepared with a growth catalyst where each carbon nanotube is simultaneously and completely filled with a conductive filler.
- The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following description taken in connection with accompanying drawings wherein like reference characters refer to like elements.
- FIG. 1a is a photograph of a scanning electron microscopy micrograph illustrating the dense and well-aligned morphology of the carbon nanotube films.
- FIG. 1b is a photograph of a scanning electron microscopy micrograph illustrating the structure of the carbon nanotubes.
- FIG. 1c is a photograph of a scanning electron microscopy micrograph illustrating a tilted carbon nanotube revealing the structure of a nanowire enclosed within.
- FIG. 2a is a photograph of a cross-sectional transmission electron microscopy illustrating the nature of the conductive fillers (nanowires) filling the core of carbon nanotubes.
- FIG. 2b is an energy-dispersive x-ray spectra illustrating that the core of the conductive filler (nanowire) is comprised of both titanium and carbon.
- FIG. 2c is a photograph of a high resolution transmission electron microscopy illustrating that the carbon walls are disordered graphite.
- The present invention is an array of a plurality of carbon nanotubes where each nanotube is attached to a substrate and extends from the substrate and has a closed outer wall defining a hollow core that is simultaneously filled more than 10% with a conductive filler while the carbon nanotube grows. The present invention further provides a method for making this array of carbon nanotubes which includes the steps of depositing a growth catalyst onto the substrate to form a prepared substrate, creating a vacuum within a vessel which contains the prepared substrate, flowing H2/inert (e.g. Ar) gas within the vessel and increasing the pressure within the vessel, increasing the temperature of the prepared substrate, and changing the H2/Ar gas to ethylene gas such that the ethylene gas flows within the vessel.
- The arrays of the carbon nanotubes filled with conductive filler are fabricated by first depositing a thin layer of growth catalyst onto a substrate. Depositing the growth catalyst is preferably by electron beam evaporation, and preferably results in a thin layer on the substrate which is about 1 to 30 nanometers in thickness. The substrate is an electrically conductive substrate, preferably made of metals including but not limited to transition elements appearing in groups IIIB, IVB, VIB, VIIB, VIII, and IB of the periodic table. Preferred metals are titanium, vanadium, tantalum, and combinations thereof. Non-metals such as carbides may also be used for the substrate, for example, titanium carbide. The growth catalyst is preferably iron, but may also be iron oxide and combinations thereof.
- After the conductive substrate is prepared with the growth catalyst coating, the vessel which contains the prepared substrate is evacuated to a first pressure below 2 torr. The vessel is preferably a quartz reactor placed within a tube furnace. The pressure within the vessel is then increased to a second pressure within the range from about 200 torr to about 400 torr by flowing H2/inert (e.g. Ar) gas within the vessel. After the pressure stabilizes within the vessel, the prepared substrate is heated using the tube furnace. Once the prepared substrate temperature reaches the growth temperature, which can range from about 650° C. to about 800° C., but which is preferably from about 700° C. to 775° C., the H2/Ar flow is stopped and ethylene gas, preferably but not necessarily with a purity of about 99.5%, is introduced into the reactor. A preferable introduction flow rate of 200 cm3/min. Typical growth periods range from about 10 minutes to 3 hours.
- The heat treatment of the prepared substrate can be controlled to vary the density and separation of catalyst particles on the prepared substrate. A higher heat results in more coalescing of the catalyst particles, and thus, fewer and larger catalyst sites, which results in separation distances between these sites on the substrate. The density of the catalyst sites controls the diameter of the carbon nanotubes with a higher density resulting in a greater diameter carbon nanotube. As the ethylene gas flows, it decomposes as a carbon source and diffuses into the catalyst particles causing precipitation and growth of the carbon nanotubes. At the same time, the substrate material diffuses into the catalyst particles resulting in the growth of a carbide core (conductive filler) within the hollow carbon nanotubes. The carbide core within the carbon nanotubes is a conductive filler preferably made up of carbon and titanium. However, the conductive filler may also be made up of carbon and whichever metal makes up the conductive substrate, which includes but is not limited to transition elements appearing in groups IIIB, IVB, VIB, VIIB, VIII, and IB of the periodic table. Preferred metals are titanium, vanadium, tantalum, and combinations thereof. The hollow core of each carbon nanotube is filled with the conductive filler to a point which is greater than 10% full, but which is preferably greater than 50% full, and which is more preferably greater than 75% full, and which is most preferably about 100% full, where “about 100%” means 100%, plus or minus 5%.
- The carbon nanotubes have lengths ranging from about 1 to 2 μm, varying no more than about 5%, which provides uniform lengths. The carbon nanotubes also have uniform diameters such that their diameters vary no more than about 5%. The outside nanotube diameter ranges from less than 40 to about 400 nm and the inside nanotube diameter ranges from about 10 to about 100 nm. The diameters of the carbon nanotubes and filled cores can be controlled by varying the thickness of the catalyst (iron) layer. In general, the thicker the iron catalyst layer, the bigger the tube diameter. However, when the tube diameter is less than 40 nm, the carbon nanotubes are curved and only partially filled.
- A number of substrates were selected to investigate their effects on the formation of the filled carbon nanotubes. The formation of the filled nanotubes depends on the solubility of the iron (the catalyst) in the substrate and the free energy of formation for the respective carbide phase. The substrates selected included tantalum, silicon, and molybdenum. All of these materials can form stable carbides. Carbon nanotubes were deposited on the substrates under the same growth conditions used for growth of carbon nanotubes on titanium substrates. While dense arrays of filled carbon nanotubes were observed on tantalum substrates similar to those shown in FIG. 1a, only curved hollow carbon nanotubes were formed on silicon substrates. No carbon nanotubes were observed on molybdenum substrates. For molybdenum substrates, X-ray photoelectron spectrometry and backscattering electron SEM indicated formation of Fe—Mo solid solutions in the surface region of the substrates. The high solubility of Fe in Mo depleted the catalytic material required to grow the carbon nanotubes. For silicon substrates, the driving force to form SiC is much lower than that for the formation of either TiC or TaC. The free energy of formation of these carbides is on the order of −43 kcal/mol for TiC, −35 kcal/mol for TaC, and −15 kcal/mol for SiC. Although carbon nanotubes are formed on silicon, the growth rate of SiC is very low compared to that of TiC or TaC, resulting in hollow carbon nanotubes. These tubes tend to be tilted or curved.
- The carbon nanotubes of the present invention are examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). FIG. 1a reveals the dense, well-aligned morphology of the carbon nanotube films. The SEM images were recorded using 70% secondary electron signals and 30% back scattering electron signals. The intensity is therefore proportional to the atomic number of the elements that comprise the material. A magnified SEM image (FIG. 1b) shows that the structure of the carbon nanotubes of the present invention is different from that of oriented carbon nanotubes previously reported. First, the carbon tubes are densely packed, rather than well separated as with prior reported carbon nanotubes. Secondly, the tube tips as shown in FIG. 's 1 a, 1 b, & 1 c, appear brighter at the center of the carbon nanotubes, indicating that the cores of the carbon nanotubes are filled with a material having elements of higher atomic number than carbon.
- Most of the carbon nanotubes filled with conductive filler of the present invention in FIG. 1a have similar length and are approximately perpendicular to the substrate surface, although in a few cases the conductive filler is tilted and extended above the film surface. A SEM image (FIG. 1c) of a tilted nanotube reveals a structure of conductive filler enclosed by carbon. The filled material has a large head near the tube tip, and its diameter is about one quarter of the carbon nanotube diameter. Further evidence of filled cores and carbon caps is provided by the cross-sectional TEM image in FIG. 2a and energy-dispersive xray (EDX) spectra illustrated in FIG. 2b. The cross-sectional TEM image in FIG. 2a shows that individual conductive filler grows continuously from the bottom to the top of the films. The filled nature of the carbon nanotubes can be clearly seen by the distinct contrast between the filled core and carbon wall. The cross-sectional TEM image in FIG. 2a reveals that the cores have a large head near the tube tip, in agreement with the SEM image (FIG. 1c). The core diameter in the cross-sectional TEM image in FIG. 2a appears slightly smaller than that observed in the SEM image (FIG. 1c), presumably due to the off-center cut of the TEM specimen. EDX analysis revealed that the walls and caps of the conductive fillers are carbon. A high-resolution TEM image (FIG. 2c) reveals that the carbon walls are disordered graphite.
- EDX analysis of the carbon nanotube and conductive filler of the present invention also indicates that the core of the conductive filler is comprised of titanium and carbon except for the region near the substrate where iron was found. Electron diffraction patterns obtained from the cores reveal that the cores are cubic TiC. The convergent beam electron diffraction pattern (inset in FIG. 2a) recorded along the <001> zone axis parallel to the electron beam exhibits a lattice spacing (˜0.43 nm) and four-fold symmetry corresponding to the (100) planes of cubic TiC. In addition, the electron diffraction patterns reveal that the TiC cores are single crystals. In the high-resolution TEM image (FIG. 2c), the interface between the graphite wall and TiC core is abrupt and free of any intermediate phase. The magnified images show well-ordered lattice fringes of the TiC core (right inset of FIG. 2c) and disordered lattice fringes of the graphite wall (left inset of FIG. 2c). It should be pointed out that this is the first time that carbon nanotubes are completely filled with metallic TiC cores.
- Moreover, all TiC cores show a big head near the tube tip (FIG. 1c and 2 a), indicating that the initial growth of the TiC cores is faster. This may be due to an initially high concentration of titanium dissolved in the iron particle during heating to the growth temperature (2.7 to 3 hours) before introducing ethylene gas into the reactor. After the initial growth, the dissolution and precipitation process reaches an equilibrium condition under which the consumed rate of titanium for the precipitation of TiC is approximately equal to the mass transfer rate of titanium into the iron particle, resulting in uniform core diameters. Carbon diffusion is not the limiting step in the formation of TiC because interstitial diffusion of carbon in iron is much faster than substitutional diffusion of titanium in iron.
- Therefore it can be concluded that growth of oriented and filled carbon nanotubes requires stable catalytic particles and low free energy of formation of a reaction product in the core.
- While a preferred embodiment of the present invention has been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover all such changes and modifications as fall within the true spirit and scope of the invention.
Claims (29)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/333,876 US6361861B2 (en) | 1999-06-14 | 1999-06-14 | Carbon nanotubes on a substrate |
AU78244/00A AU7824400A (en) | 1999-06-14 | 2000-06-13 | Carbon nanotubes on a substrate and method of making |
PCT/US2000/016783 WO2000076912A2 (en) | 1999-06-14 | 2000-06-13 | Carbon nanotubes on a substrate and method of making |
US09/996,523 US7011771B2 (en) | 1999-06-14 | 2001-11-28 | Method of making carbon nanotubes on a substrate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/333,876 US6361861B2 (en) | 1999-06-14 | 1999-06-14 | Carbon nanotubes on a substrate |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/996,523 Division US7011771B2 (en) | 1999-06-14 | 2001-11-28 | Method of making carbon nanotubes on a substrate |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020004136A1 true US20020004136A1 (en) | 2002-01-10 |
US6361861B2 US6361861B2 (en) | 2002-03-26 |
Family
ID=23304630
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/333,876 Expired - Lifetime US6361861B2 (en) | 1999-06-14 | 1999-06-14 | Carbon nanotubes on a substrate |
US09/996,523 Expired - Lifetime US7011771B2 (en) | 1999-06-14 | 2001-11-28 | Method of making carbon nanotubes on a substrate |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/996,523 Expired - Lifetime US7011771B2 (en) | 1999-06-14 | 2001-11-28 | Method of making carbon nanotubes on a substrate |
Country Status (3)
Country | Link |
---|---|
US (2) | US6361861B2 (en) |
AU (1) | AU7824400A (en) |
WO (1) | WO2000076912A2 (en) |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6423583B1 (en) * | 2001-01-03 | 2002-07-23 | International Business Machines Corporation | Methodology for electrically induced selective breakdown of nanotubes |
US20040039717A1 (en) * | 2002-08-22 | 2004-02-26 | Alex Nugent | High-density synapse chip using nanoparticles |
US20040153426A1 (en) * | 2002-03-12 | 2004-08-05 | Alex Nugent | Physical neural network liquid state machine utilizing nanotechnology |
US6863852B1 (en) | 2002-05-30 | 2005-03-08 | Zeus Industrial Products, Inc. | Fluoropolymer extrusions based on novel combinations of process parameters and clay minerals |
EP1528042A1 (en) * | 2003-09-25 | 2005-05-04 | Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. | Method of producing nanostructured magnetic functional elements |
US20050149464A1 (en) * | 2002-03-12 | 2005-07-07 | Knowmtech, Llc. | Pattern recognition utilizing a nanotechnology-based neural network |
US20050279274A1 (en) * | 2004-04-30 | 2005-12-22 | Chunming Niu | Systems and methods for nanowire growth and manufacturing |
US20060057767A1 (en) * | 2004-03-22 | 2006-03-16 | Regan Brian C | Nanoscale mass conveyors |
US20060117797A1 (en) * | 2004-12-08 | 2006-06-08 | Hon Hai Precision Industry Co., Ltd. | Composite mold for molding glass lens |
US20060141153A1 (en) * | 2002-06-24 | 2006-06-29 | Honda Giken Kogyo Kabushiki Kaisha | Method for making carbon nanotubes |
US20060184466A1 (en) * | 2005-01-31 | 2006-08-17 | Alex Nugent | Fractal memory and computational methods and systems based on nanotechnology |
US20060252276A1 (en) * | 2002-02-09 | 2006-11-09 | Samsung Electronics Co., Ltd. | Method of fabricating memory device utilizing carbon nanotubes |
US20070005532A1 (en) * | 2005-05-23 | 2007-01-04 | Alex Nugent | Plasticity-induced self organizing nanotechnology for the extraction of independent components from a data stream |
US20070110971A1 (en) * | 2003-04-17 | 2007-05-17 | Anne-Marie Bonnot | Carbon nanotube growth method |
US20070176643A1 (en) * | 2005-06-17 | 2007-08-02 | Alex Nugent | Universal logic gate utilizing nanotechnology |
US20070243717A1 (en) * | 2004-11-29 | 2007-10-18 | Francisco Santiago | Carbon nanotube apparatus and method of carbon nanotube modification |
US7398259B2 (en) | 2002-03-12 | 2008-07-08 | Knowmtech, Llc | Training of a physical neural network |
US7412428B2 (en) | 2002-03-12 | 2008-08-12 | Knowmtech, Llc. | Application of hebbian and anti-hebbian learning to nanotechnology-based physical neural networks |
US20080197339A1 (en) * | 2004-10-04 | 2008-08-21 | Brian Christopher Regan | Nanocrystal powered nanomotor |
US7426501B2 (en) | 2003-07-18 | 2008-09-16 | Knowntech, Llc | Nanotechnology neural network methods and systems |
US20090043722A1 (en) * | 2003-03-27 | 2009-02-12 | Alex Nugent | Adaptive neural network utilizing nanotechnology-based components |
US20090228416A1 (en) * | 2002-08-22 | 2009-09-10 | Alex Nugent | High density synapse chip using nanoparticles |
US20090228415A1 (en) * | 2002-06-05 | 2009-09-10 | Alex Nugent | Multilayer training in a physical neural network formed utilizing nanotechnology |
US7599895B2 (en) | 2005-07-07 | 2009-10-06 | Knowm Tech, Llc | Methodology for the configuration and repair of unreliable switching elements |
US20090277609A1 (en) * | 2008-05-07 | 2009-11-12 | The Regents Of The University Of California | Tunable Thermal Link |
US7930257B2 (en) | 2007-01-05 | 2011-04-19 | Knowm Tech, Llc | Hierarchical temporal memory utilizing nanotechnology |
US20110183139A1 (en) * | 2006-05-01 | 2011-07-28 | Leonid Grigorian | Organized carbon and non-carbon assembly |
US20110183155A1 (en) * | 2010-01-22 | 2011-07-28 | Toyota Jidosha Kabushiki Kaisha | Mold, solidified body, and methods of manufacture thereof |
US8487028B2 (en) * | 2000-07-31 | 2013-07-16 | Los Alamos National Security, Llc | Polymer-assisted deposition of films and preparation of carbon nanotube arrays using the films |
US8623288B1 (en) | 2009-06-29 | 2014-01-07 | Nanosys, Inc. | Apparatus and methods for high density nanowire growth |
US20150147573A1 (en) * | 2004-11-09 | 2015-05-28 | Board Of Regents, The University Of Texas System | Nanofiber ribbons and sheets and fabrication and application thereof |
US9269043B2 (en) | 2002-03-12 | 2016-02-23 | Knowm Tech, Llc | Memristive neural processor utilizing anti-hebbian and hebbian technology |
WO2019023455A1 (en) * | 2017-07-28 | 2019-01-31 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
US10815124B2 (en) | 2012-07-12 | 2020-10-27 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
Families Citing this family (237)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7576027B2 (en) * | 1999-01-12 | 2009-08-18 | Hyperion Catalysis International, Inc. | Methods of making carbide and oxycarbide containing catalysts |
US6913075B1 (en) * | 1999-06-14 | 2005-07-05 | Energy Science Laboratories, Inc. | Dendritic fiber material |
US20040009353A1 (en) * | 1999-06-14 | 2004-01-15 | Knowles Timothy R. | PCM/aligned fiber composite thermal interface |
US7132161B2 (en) * | 1999-06-14 | 2006-11-07 | Energy Science Laboratories, Inc. | Fiber adhesive material |
US6689439B2 (en) * | 2000-03-08 | 2004-02-10 | Zbigniew S. Sobolewski | Micro-stud diffusion substrate for use in fuel cells |
DE10036897C1 (en) * | 2000-07-28 | 2002-01-03 | Infineon Technologies Ag | Field effect transistor used in a switching arrangement comprises a gate region between a source region and a drain region |
EP2360298A3 (en) * | 2000-08-22 | 2011-10-05 | President and Fellows of Harvard College | Method for depositing a semiconductor nanowire |
US20060175601A1 (en) * | 2000-08-22 | 2006-08-10 | President And Fellows Of Harvard College | Nanoscale wires and related devices |
JP2002201014A (en) * | 2000-10-30 | 2002-07-16 | Honda Motor Co Ltd | Method for producing carbon nanotube |
JP3737696B2 (en) * | 2000-11-17 | 2006-01-18 | 株式会社東芝 | Method for manufacturing horizontal field emission cold cathode device |
US6885022B2 (en) * | 2000-12-08 | 2005-04-26 | Si Diamond Technology, Inc. | Low work function material |
US20050200261A1 (en) * | 2000-12-08 | 2005-09-15 | Nano-Proprietary, Inc. | Low work function cathode |
AU2904602A (en) | 2000-12-11 | 2002-06-24 | Harvard College | Nanosensors |
EP1384322A1 (en) * | 2001-03-30 | 2004-01-28 | California Institute Of Technology | Carbon nanotube array rf filter |
CN1306619C (en) | 2001-03-30 | 2007-03-21 | 加利福尼亚大学董事会 | Methods of fabricating nanostructures and nanowires and devices fabricated therefrom |
AU2002245939B2 (en) * | 2001-04-04 | 2006-05-11 | Commonwealth Scientific And Industrial Research Organisation | Process and apparatus for the production of carbon nanotubes |
AUPR421701A0 (en) * | 2001-04-04 | 2001-05-17 | Commonwealth Scientific And Industrial Research Organisation | Process and apparatus for the production of carbon nanotubes |
WO2002088025A1 (en) * | 2001-04-26 | 2002-11-07 | New York University | Method for dissolving carbon nanotubes |
US6911767B2 (en) | 2001-06-14 | 2005-06-28 | Hyperion Catalysis International, Inc. | Field emission devices using ion bombarded carbon nanotubes |
US7341498B2 (en) | 2001-06-14 | 2008-03-11 | Hyperion Catalysis International, Inc. | Method of irradiating field emission cathode having nanotubes |
EP1451844A4 (en) | 2001-06-14 | 2008-03-12 | Hyperion Catalysis Int | Field emission devices using modified carbon nanotubes |
US6835591B2 (en) * | 2001-07-25 | 2004-12-28 | Nantero, Inc. | Methods of nanotube films and articles |
US6643165B2 (en) | 2001-07-25 | 2003-11-04 | Nantero, Inc. | Electromechanical memory having cell selection circuitry constructed with nanotube technology |
US7566478B2 (en) * | 2001-07-25 | 2009-07-28 | Nantero, Inc. | Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles |
US7259410B2 (en) * | 2001-07-25 | 2007-08-21 | Nantero, Inc. | Devices having horizontally-disposed nanofabric articles and methods of making the same |
US6706402B2 (en) | 2001-07-25 | 2004-03-16 | Nantero, Inc. | Nanotube films and articles |
US6919592B2 (en) * | 2001-07-25 | 2005-07-19 | Nantero, Inc. | Electromechanical memory array using nanotube ribbons and method for making same |
US6924538B2 (en) * | 2001-07-25 | 2005-08-02 | Nantero, Inc. | Devices having vertically-disposed nanofabric articles and methods of making the same |
US6574130B2 (en) * | 2001-07-25 | 2003-06-03 | Nantero, Inc. | Hybrid circuit having nanotube electromechanical memory |
JP3768937B2 (en) * | 2001-09-10 | 2006-04-19 | キヤノン株式会社 | Electron emitting device, electron source, and manufacturing method of image display device |
US6599808B2 (en) * | 2001-09-12 | 2003-07-29 | Intel Corporation | Method and device for on-chip decoupling capacitor using nanostructures as bottom electrode |
US7588699B2 (en) * | 2001-11-02 | 2009-09-15 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof |
US6645628B2 (en) | 2001-11-13 | 2003-11-11 | The United States Of America As Represented By The Secretary Of The Air Force | Carbon nanotube coated anode |
SG106651A1 (en) * | 2001-11-27 | 2004-10-29 | Univ Nanyang | Field emission device and method of fabricating same |
GB2384008B (en) | 2001-12-12 | 2005-07-20 | Electrovac | Method of synthesising carbon nano tubes |
US7820132B2 (en) * | 2001-12-14 | 2010-10-26 | Alliance For Sustainable Energy, Llc | Hot wire production of single-wall and multi-wall carbon nanotubes |
US20040265211A1 (en) * | 2001-12-14 | 2004-12-30 | Dillon Anne C. | Hot wire production of single-wall carbon nanotubes |
US6713519B2 (en) * | 2001-12-21 | 2004-03-30 | Battelle Memorial Institute | Carbon nanotube-containing catalysts, methods of making, and reactions catalyzed over nanotube catalysts |
EP1465836A2 (en) | 2001-12-21 | 2004-10-13 | Battelle Memorial Institute | Structures containing carbon nanotubes and a porous support, methods of making the same, and related uses |
US7176505B2 (en) * | 2001-12-28 | 2007-02-13 | Nantero, Inc. | Electromechanical three-trace junction devices |
US6784028B2 (en) | 2001-12-28 | 2004-08-31 | Nantero, Inc. | Methods of making electromechanical three-trace junction devices |
US20040225213A1 (en) * | 2002-01-22 | 2004-11-11 | Xingwu Wang | Magnetic resonance imaging coated assembly |
US20050260331A1 (en) * | 2002-01-22 | 2005-11-24 | Xingwu Wang | Process for coating a substrate |
US20040052928A1 (en) * | 2002-09-06 | 2004-03-18 | Ehud Gazit | Peptides and methods using same for diagnosing and treating amyloid-associated diseases |
US7781396B2 (en) * | 2002-01-31 | 2010-08-24 | Tel Aviv University Future Technology Development L.P. | Peptides directed for diagnosis and treatment of amyloid-associated disease |
US7115305B2 (en) * | 2002-02-01 | 2006-10-03 | California Institute Of Technology | Method of producing regular arrays of nano-scale objects using nano-structured block-copolymeric materials |
JP3686941B2 (en) * | 2002-02-04 | 2005-08-24 | 独立行政法人物質・材料研究機構 | Nano thermometer and manufacturing method thereof |
US6515325B1 (en) | 2002-03-06 | 2003-02-04 | Micron Technology, Inc. | Nanotube semiconductor devices and methods for making the same |
US6872645B2 (en) * | 2002-04-02 | 2005-03-29 | Nanosys, Inc. | Methods of positioning and/or orienting nanostructures |
US6831017B1 (en) * | 2002-04-05 | 2004-12-14 | Integrated Nanosystems, Inc. | Catalyst patterning for nanowire devices |
CA2385802C (en) * | 2002-05-09 | 2008-09-02 | Institut National De La Recherche Scientifique | Method and apparatus for producing single-wall carbon nanotubes |
CN1248959C (en) * | 2002-09-17 | 2006-04-05 | 清华大学 | Carbon nano pipe array growth method |
JP2005261988A (en) * | 2002-09-20 | 2005-09-29 | Andes Denki Kk | Photocatalyst material and its manufacturing method |
US7253434B2 (en) * | 2002-10-29 | 2007-08-07 | President And Fellows Of Harvard College | Suspended carbon nanotube field effect transistor |
EP1560792B1 (en) * | 2002-10-29 | 2014-07-30 | President and Fellows of Harvard College | Carbon nanotube device fabrication |
DE10250829B4 (en) * | 2002-10-31 | 2006-11-02 | Infineon Technologies Ag | Nonvolatile memory cell, memory cell array, and method of making a nonvolatile memory cell |
US20040097371A1 (en) * | 2002-11-19 | 2004-05-20 | Juzer Jangbarwala | Application of conductive adsorbents, activated carbon granules and carbon fibers as substrates in catalysis |
US7162308B2 (en) | 2002-11-26 | 2007-01-09 | Wilson Greatbatch Technologies, Inc. | Nanotube coatings for implantable electrodes |
JP3921533B2 (en) * | 2002-12-04 | 2007-05-30 | 独立行政法人物質・材料研究機構 | Temperature sensing element, manufacturing method thereof, and nano thermometer |
US7596415B2 (en) | 2002-12-06 | 2009-09-29 | Medtronic, Inc. | Medical devices incorporating carbon nanotube material and methods of fabricating same |
US7844347B2 (en) * | 2002-12-06 | 2010-11-30 | Medtronic, Inc. | Medical devices incorporating carbon nanotube material and methods of fabricating same |
US7491699B2 (en) | 2002-12-09 | 2009-02-17 | Ramot At Tel Aviv University Ltd. | Peptide nanostructures and methods of generating and using the same |
WO2004059298A1 (en) * | 2002-12-20 | 2004-07-15 | Rensselaer Polytechnic Institute | Miniaturized gas sensors featuring electrical breakdown in the vicinity of carbon nanotube tips |
AU2003299854A1 (en) * | 2002-12-20 | 2004-07-22 | Alnaire Laboratories Corporation | Optical pulse lasers |
CN1286715C (en) * | 2002-12-21 | 2006-11-29 | 清华大学 | Carbon nanometer tube array structure and growing method thereof |
WO2004060791A1 (en) * | 2003-01-07 | 2004-07-22 | Ramot At Tel Aviv University Ltd. | Peptide nanostructures encapsulating a foreign material and method of manufacturing same |
US7560136B2 (en) * | 2003-01-13 | 2009-07-14 | Nantero, Inc. | Methods of using thin metal layers to make carbon nanotube films, layers, fabrics, ribbons, elements and articles |
CN1720346B (en) * | 2003-01-13 | 2011-12-21 | 南泰若股份有限公司 | Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles |
WO2004065926A1 (en) * | 2003-01-23 | 2004-08-05 | William Marsh Rice University | Smart materials: strain sensing and stress determination by means of nanotube sensing systems, composites, and devices |
US7316061B2 (en) * | 2003-02-03 | 2008-01-08 | Intel Corporation | Packaging of integrated circuits with carbon nano-tube arrays to enhance heat dissipation through a thermal interface |
US20060184843A1 (en) * | 2003-02-14 | 2006-08-17 | Oakley William S | Data recording using carbon nanotube electron sources |
CN1286716C (en) * | 2003-03-19 | 2006-11-29 | 清华大学 | Method for growing carbon nano tube |
US20050155779A1 (en) * | 2003-04-08 | 2005-07-21 | Xingwu Wang | Coated substrate assembly |
US20050038498A1 (en) * | 2003-04-17 | 2005-02-17 | Nanosys, Inc. | Medical device applications of nanostructured surfaces |
US7579077B2 (en) * | 2003-05-05 | 2009-08-25 | Nanosys, Inc. | Nanofiber surfaces for use in enhanced surface area applications |
US7972616B2 (en) * | 2003-04-17 | 2011-07-05 | Nanosys, Inc. | Medical device applications of nanostructured surfaces |
US7803574B2 (en) * | 2003-05-05 | 2010-09-28 | Nanosys, Inc. | Medical device applications of nanostructured surfaces |
TWI427709B (en) * | 2003-05-05 | 2014-02-21 | Nanosys Inc | Nanofiber surfaces for use in enhanced surface area applications |
US7780918B2 (en) * | 2003-05-14 | 2010-08-24 | Nantero, Inc. | Sensor platform using a horizontally oriented nanotube element |
DE10324081B4 (en) * | 2003-05-27 | 2005-11-17 | Infineon Technologies Ag | Storage device for storing electrical charge and method for producing the same |
US7384792B1 (en) * | 2003-05-27 | 2008-06-10 | Opto Trace Technologies, Inc. | Method of fabricating nano-structured surface and configuration of surface enhanced light scattering probe |
US8081308B2 (en) * | 2003-05-27 | 2011-12-20 | Optotrace Technologies, Inc. | Detecting chemical and biological impurities by nano-structure based spectral sensing |
US7956997B2 (en) * | 2003-05-27 | 2011-06-07 | Optotrace Technologies, Inc. | Systems and methods for food safety detection |
US8102525B2 (en) * | 2008-10-07 | 2012-01-24 | OptoTrace (SuZhou) Technologies, Inc. | Systems and methods for detecting chemical and biological substances |
US8213007B2 (en) * | 2003-05-27 | 2012-07-03 | Optotrace Technologies, Inc. | Spectrally sensing chemical and biological substances |
US8031335B2 (en) * | 2003-05-27 | 2011-10-04 | Opto Trace Technologies, Inc. | Non-invasive disease diagnosis using light scattering probe |
US7118941B2 (en) * | 2003-06-25 | 2006-10-10 | Intel Corporation | Method of fabricating a composite carbon nanotube thermal interface device |
US7112472B2 (en) * | 2003-06-25 | 2006-09-26 | Intel Corporation | Methods of fabricating a composite carbon nanotube thermal interface device |
CA2530927A1 (en) * | 2003-06-30 | 2005-01-06 | Tel Aviv University Future Technology Development L.P. | Peptides antibodies directed thereagainst and methods using same for diagnosing and treating amyloid-associated diseases |
US20060187802A1 (en) * | 2003-07-03 | 2006-08-24 | Oakley William S | Array of cnt heads |
WO2005067585A2 (en) * | 2003-07-03 | 2005-07-28 | William Oakley | Adaptive read and read-after-write for carbon nanotube recorders |
CA2536896A1 (en) * | 2003-07-08 | 2005-01-20 | Qunano Ab | Probe structures incorporating nanowhiskers, production methods thereof, and methods of forming nanowhiskers |
WO2005052179A2 (en) * | 2003-08-13 | 2005-06-09 | The Johns Hopkins University | Method of making carbon nanotube arrays, and thermal interfaces using same |
WO2005019104A2 (en) * | 2003-08-18 | 2005-03-03 | President And Fellows Of Harvard College | Controlled nanotube fabrication and uses |
US7477527B2 (en) * | 2005-03-21 | 2009-01-13 | Nanoconduction, Inc. | Apparatus for attaching a cooling structure to an integrated circuit |
US20070126116A1 (en) * | 2004-08-24 | 2007-06-07 | Carlos Dangelo | Integrated Circuit Micro-Cooler Having Tubes of a CNT Array in Essentially the Same Height over a Surface |
US7538422B2 (en) * | 2003-08-25 | 2009-05-26 | Nanoconduction Inc. | Integrated circuit micro-cooler having multi-layers of tubes of a CNT array |
US7732918B2 (en) * | 2003-08-25 | 2010-06-08 | Nanoconduction, Inc. | Vapor chamber heat sink having a carbon nanotube fluid interface |
US20070114658A1 (en) * | 2004-08-24 | 2007-05-24 | Carlos Dangelo | Integrated Circuit Micro-Cooler with Double-Sided Tubes of a CNT Array |
US7109581B2 (en) * | 2003-08-25 | 2006-09-19 | Nanoconduction, Inc. | System and method using self-assembled nano structures in the design and fabrication of an integrated circuit micro-cooler |
US8048688B2 (en) * | 2006-10-24 | 2011-11-01 | Samsung Electronics Co., Ltd. | Method and apparatus for evaluation and improvement of mechanical and thermal properties of CNT/CNF arrays |
EP1663199B1 (en) * | 2003-09-25 | 2013-04-03 | Tel Aviv University Future Technology Development L.P. | Compositions and methods using same for treating amyloid-associated diseases |
US7625707B2 (en) * | 2003-10-02 | 2009-12-01 | Ramot At Tel Aviv University Ltd. | Antibacterial agents and methods of identifying and utilizing same |
WO2005084172A2 (en) * | 2003-10-03 | 2005-09-15 | College Of William & Mary | Carbon nanostructures and methods of making and using the same |
WO2005044723A2 (en) * | 2003-10-16 | 2005-05-19 | The University Of Akron | Carbon nanotubes on carbon nanofiber substrate |
FR2864528B1 (en) * | 2003-12-31 | 2006-12-15 | Total France | PROCESS FOR TREATING METHANE / CARBON DIOXIDE MIXTURES |
FR2864532B1 (en) * | 2003-12-31 | 2007-04-13 | Total France | PROCESS FOR TRANSFORMING A SYNTHETIC GAS TO HYDROCARBONS IN THE PRESENCE OF SIC BETA AND EFFLUTING THE SAME |
US7144563B2 (en) * | 2004-04-22 | 2006-12-05 | Clemson University | Synthesis of branched carbon nanotubes |
US20050238810A1 (en) * | 2004-04-26 | 2005-10-27 | Mainstream Engineering Corp. | Nanotube/metal substrate composites and methods for producing such composites |
US7491628B2 (en) * | 2004-05-05 | 2009-02-17 | California Institute Of Technology | Method for patterning large scale nano-fibrous surfaces using capillography |
US7335408B2 (en) * | 2004-05-14 | 2008-02-26 | Fujitsu Limited | Carbon nanotube composite material comprising a continuous metal coating in the inner surface, magnetic material and production thereof |
US20050260412A1 (en) * | 2004-05-19 | 2005-11-24 | Lockheed Martin Corporation | System, method, and apparatus for producing high efficiency heat transfer device with carbon nanotubes |
US20090156471A1 (en) * | 2004-07-15 | 2009-06-18 | Ramot At Tel Aviv University Ltd. | Use of anti-amyloid agents for treating and typing pathogen infections |
US7129097B2 (en) * | 2004-07-29 | 2006-10-31 | International Business Machines Corporation | Integrated circuit chip utilizing oriented carbon nanotube conductive layers |
WO2006013552A2 (en) | 2004-08-02 | 2006-02-09 | Ramot At Tel Aviv University Ltd. | Articles of peptide nanostructures and method of forming the same |
WO2006018850A2 (en) * | 2004-08-19 | 2006-02-23 | Tel Aviv University Future Technology Development L.P. | Compositions for treating amyloid associated diseases |
US7786086B2 (en) * | 2004-09-08 | 2010-08-31 | Ramot At Tel-Aviv University Ltd. | Peptide nanostructures containing end-capping modified peptides and methods of generating and using the same |
US7158219B2 (en) * | 2004-09-16 | 2007-01-02 | Hewlett-Packard Development Company, L.P. | SERS-active structures including nanowires |
US8471238B2 (en) * | 2004-09-16 | 2013-06-25 | Nantero Inc. | Light emitters using nanotubes and methods of making same |
US7233071B2 (en) * | 2004-10-04 | 2007-06-19 | International Business Machines Corporation | Low-k dielectric layer based upon carbon nanostructures |
US20060083927A1 (en) * | 2004-10-15 | 2006-04-20 | Zyvex Corporation | Thermal interface incorporating nanotubes |
US20080090183A1 (en) * | 2004-10-22 | 2008-04-17 | Lingbo Zhu | Aligned Carbon Nanotubes And Method For Construction Thereof |
US8021967B2 (en) * | 2004-11-01 | 2011-09-20 | California Institute Of Technology | Nanoscale wicking methods and devices |
US20080012461A1 (en) * | 2004-11-09 | 2008-01-17 | Nano-Proprietary, Inc. | Carbon nanotube cold cathode |
US20060096870A1 (en) * | 2004-11-10 | 2006-05-11 | Fwu-Shan Sheu | Detection of biological molecules |
US8278011B2 (en) | 2004-12-09 | 2012-10-02 | Nanosys, Inc. | Nanostructured catalyst supports |
US7939218B2 (en) * | 2004-12-09 | 2011-05-10 | Nanosys, Inc. | Nanowire structures comprising carbon |
CN101707256B (en) | 2004-12-09 | 2013-11-06 | 奈米系统股份有限公司 | Nanowire-based membrane electrode assemblies for fuel cells |
US7842432B2 (en) * | 2004-12-09 | 2010-11-30 | Nanosys, Inc. | Nanowire structures comprising carbon |
TWI324024B (en) * | 2005-01-14 | 2010-04-21 | Hon Hai Prec Ind Co Ltd | Field emission type light source |
CA2500766A1 (en) * | 2005-03-14 | 2006-09-14 | National Research Council Of Canada | Method and apparatus for the continuous production and functionalization of single-walled carbon nanotubes using a high frequency induction plasma torch |
CN101203740B (en) * | 2005-04-06 | 2011-03-23 | 哈佛大学校长及研究员协会 | Molecular identification with carbon nanotube control |
CN100500555C (en) * | 2005-04-15 | 2009-06-17 | 清华大学 | Carbon nanotube array structure and its preparation process |
US7989349B2 (en) | 2005-04-15 | 2011-08-02 | Micron Technology, Inc. | Methods of manufacturing nanotubes having controlled characteristics |
US7754183B2 (en) * | 2005-05-20 | 2010-07-13 | Clemson University Research Foundation | Process for preparing carbon nanostructures with tailored properties and products utilizing same |
US7767616B2 (en) * | 2005-05-26 | 2010-08-03 | Uchicago Argonne, Llc | Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction |
WO2006132659A2 (en) * | 2005-06-06 | 2006-12-14 | President And Fellows Of Harvard College | Nanowire heterostructures |
US20060286024A1 (en) * | 2005-06-15 | 2006-12-21 | Baker R Terry K | Synthesis and cleaving of carbon nanochips |
US10004828B2 (en) * | 2005-10-11 | 2018-06-26 | Romat at Tel-Aviv University Ltd. | Self-assembled Fmoc-ff hydrogels |
US7879212B2 (en) * | 2005-11-03 | 2011-02-01 | Ramot At Tel-Aviv University Ltd. | Peptide nanostructure-coated electrodes |
CN1962427B (en) * | 2005-11-09 | 2010-11-10 | 鸿富锦精密工业(深圳)有限公司 | Production method of nano-carbon tube |
CA2624776C (en) * | 2005-11-21 | 2015-05-12 | Nanosys, Inc. | Nanowire structures comprising carbon |
US9182352B2 (en) | 2005-12-19 | 2015-11-10 | OptoTrace (SuZhou) Technologies, Inc. | System and method for detecting oil or gas underground using light scattering spectral analyses |
US7635503B2 (en) * | 2006-02-21 | 2009-12-22 | Intel Corporation | Composite metal films and carbon nanotube fabrication |
JP2007268692A (en) * | 2006-03-31 | 2007-10-18 | Fujitsu Ltd | Carbon nanotube connected body, its manufacturing method, and element and method for detecting target |
US7790243B2 (en) * | 2006-07-19 | 2010-09-07 | The Aerospace Corporation | Method for producing large-diameter 3D carbon nano-onion structures at room temperature |
DE102006047691A1 (en) * | 2006-10-09 | 2008-04-17 | Siemens Audiologische Technik Gmbh | Absorption of electromagnetic radiation in hearing aids |
US7852612B2 (en) * | 2006-10-30 | 2010-12-14 | College Of William And Mary | Supercapacitor using carbon nanosheets as electrode |
US8951631B2 (en) | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused metal fiber materials and process therefor |
US20100279569A1 (en) * | 2007-01-03 | 2010-11-04 | Lockheed Martin Corporation | Cnt-infused glass fiber materials and process therefor |
US8951632B2 (en) * | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
US9005755B2 (en) | 2007-01-03 | 2015-04-14 | Applied Nanostructured Solutions, Llc | CNS-infused carbon nanomaterials and process therefor |
US20120189846A1 (en) * | 2007-01-03 | 2012-07-26 | Lockheed Martin Corporation | Cnt-infused ceramic fiber materials and process therefor |
US8158217B2 (en) * | 2007-01-03 | 2012-04-17 | Applied Nanostructured Solutions, Llc | CNT-infused fiber and method therefor |
JP4272700B2 (en) * | 2007-01-18 | 2009-06-03 | パナソニック株式会社 | Nanostructure and manufacturing method thereof |
JP5196384B2 (en) * | 2007-03-15 | 2013-05-15 | 矢崎総業株式会社 | Capacitor comprising an organized assembly of carbon and non-carbon compounds |
US7897529B2 (en) | 2007-03-23 | 2011-03-01 | Lydall, Inc. | Substrate for carrying catalytic particles |
US8958070B2 (en) | 2007-05-29 | 2015-02-17 | OptoTrace (SuZhou) Technologies, Inc. | Multi-layer variable micro structure for sensing substance |
US20090011241A1 (en) * | 2007-07-07 | 2009-01-08 | College Of William And Mary | Carbon Nanoflake Compositions and Methods of Production |
US20090081441A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Fiber Tow Comprising Carbon-Nanotube-Infused Fibers |
US20090081383A1 (en) * | 2007-09-20 | 2009-03-26 | Lockheed Martin Corporation | Carbon Nanotube Infused Composites via Plasma Processing |
US8470408B2 (en) * | 2007-10-02 | 2013-06-25 | President And Fellows Of Harvard College | Carbon nanotube synthesis for nanopore devices |
KR20100097146A (en) * | 2007-11-15 | 2010-09-02 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Protection of carbon nanotubes |
US8515557B2 (en) | 2007-11-19 | 2013-08-20 | Cochlear Limited | Electrode array for a cochlear implant |
US8319002B2 (en) * | 2007-12-06 | 2012-11-27 | Nanosys, Inc. | Nanostructure-enhanced platelet binding and hemostatic structures |
JP5519524B2 (en) | 2007-12-06 | 2014-06-11 | ナノシス・インク. | Absorbable nano-reinforced hemostatic structure and bandage material |
US7479590B1 (en) * | 2008-01-03 | 2009-01-20 | International Business Machines Corporation | Dry adhesives, methods of manufacture thereof and articles comprising the same |
US20110102002A1 (en) * | 2008-04-09 | 2011-05-05 | Riehl Bill L | Electrode and sensor having carbon nanostructures |
US20100252450A1 (en) * | 2008-04-09 | 2010-10-07 | Riehl Bill L | Electrode and sensor having carbon nanostructures |
AU2009233885B2 (en) * | 2008-04-09 | 2013-05-30 | Riehl-Johnson Holdings, Llc | Method for production of carbon nanostructures |
CN101671442A (en) * | 2008-09-12 | 2010-03-17 | 清华大学 | Preparation method of carbon nano tube array composite material |
US8354291B2 (en) | 2008-11-24 | 2013-01-15 | University Of Southern California | Integrated circuits based on aligned nanotubes |
WO2010144161A2 (en) * | 2009-02-17 | 2010-12-16 | Lockheed Martin Corporation | Composites comprising carbon nanotubes on fiber |
JP5753102B2 (en) * | 2009-02-27 | 2015-07-22 | アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニーApplied Nanostructuredsolutions, Llc | Low temperature CNT growth using gas preheating method |
US20100224129A1 (en) * | 2009-03-03 | 2010-09-09 | Lockheed Martin Corporation | System and method for surface treatment and barrier coating of fibers for in situ cnt growth |
WO2010117515A1 (en) * | 2009-04-10 | 2010-10-14 | Lockheed Martin Corporation | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
US20100272891A1 (en) * | 2009-04-10 | 2010-10-28 | Lockheed Martin Corporation | Apparatus and method for the production of carbon nanotubes on a continuously moving substrate |
CN102388172B (en) * | 2009-04-10 | 2015-02-11 | 应用纳米结构方案公司 | Method and apparatus for using a vertical furnace to infuse carbon nanotubes to fiber |
EP2419553A4 (en) | 2009-04-17 | 2014-03-12 | Seerstone Llc | Method for producing solid carbon by reducing carbon oxides |
US9111658B2 (en) | 2009-04-24 | 2015-08-18 | Applied Nanostructured Solutions, Llc | CNS-shielded wires |
WO2010124260A1 (en) * | 2009-04-24 | 2010-10-28 | Lockheed Martin Corporation | Cnt-infused emi shielding composite and coating |
KR101696207B1 (en) * | 2009-04-27 | 2017-01-13 | 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. | Cnt-based resistive heating for deicing composite structures |
AU2010241850B2 (en) * | 2009-04-30 | 2015-03-19 | Applied Nanostructured Solutions, Llc. | Method and system for close proximity catalysis for carbon nanotube synthesis |
US20120081703A1 (en) * | 2009-05-07 | 2012-04-05 | Nant Holdings Ip, Llc | Highly Efficient Plamonic Devices, Molecule Detection Systems, and Methods of Making the Same |
EP2433475B1 (en) | 2009-05-19 | 2021-04-21 | OneD Material, Inc. | Nanostructured materials for battery applications |
WO2010148322A1 (en) | 2009-06-19 | 2010-12-23 | Under Armour, Inc. | Nanoadhesion structures for sporting gear |
US8969225B2 (en) * | 2009-08-03 | 2015-03-03 | Applied Nano Structured Soultions, LLC | Incorporation of nanoparticles in composite fibers |
AU2010313129A1 (en) * | 2009-11-02 | 2012-05-24 | Applied Nanostructured Solutions, Llc | CNT-infused aramid fiber materials and process therefor |
US20110101302A1 (en) * | 2009-11-05 | 2011-05-05 | University Of Southern California | Wafer-scale fabrication of separated carbon nanotube thin-film transistors |
AU2010350690A1 (en) * | 2009-11-23 | 2012-04-19 | Applied Nanostructured Solutions, Llc | CNT-tailored composite air-based structures |
BR112012010907A2 (en) * | 2009-11-23 | 2019-09-24 | Applied Nanostructured Sols | "Ceramic composite materials containing carbon nanotube infused fiber materials and methods for their production" |
US20110123735A1 (en) * | 2009-11-23 | 2011-05-26 | Applied Nanostructured Solutions, Llc | Cnt-infused fibers in thermoset matrices |
KR20120104600A (en) * | 2009-12-14 | 2012-09-21 | 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. | Flame-resistant composite materials and articles containing carbon nanotube-infused fiber materials |
US9167736B2 (en) * | 2010-01-15 | 2015-10-20 | Applied Nanostructured Solutions, Llc | CNT-infused fiber as a self shielding wire for enhanced power transmission line |
EP2531558B1 (en) * | 2010-02-02 | 2018-08-22 | Applied NanoStructured Solutions, LLC | Carbon nanotube-infused fiber materials containing parallel-aligned carbon nanotubes, methods for production thereof, and composite materials derived therefrom |
KR101787645B1 (en) | 2010-03-02 | 2017-10-23 | 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. | Spiral wound electrical devices containing carbon nanotube-infused electrode materials and methods and apparatuses for production thereof |
WO2011109485A1 (en) * | 2010-03-02 | 2011-09-09 | Applied Nanostructured Solutions,Llc | Electrical devices containing carbon nanotube-infused fibers and methods for production thereof |
JP5571994B2 (en) * | 2010-03-30 | 2014-08-13 | 株式会社東芝 | Carbon nanotube aggregate, solar cell, and substrate with waveguide and carbon nanotube aggregate |
CA2712051A1 (en) * | 2010-08-12 | 2012-02-12 | The Governors Of The University Of Alberta | Method of fabricating a carbon nanotube array |
US8780526B2 (en) | 2010-06-15 | 2014-07-15 | Applied Nanostructured Solutions, Llc | Electrical devices containing carbon nanotube-infused fibers and methods for production thereof |
US9017854B2 (en) | 2010-08-30 | 2015-04-28 | Applied Nanostructured Solutions, Llc | Structural energy storage assemblies and methods for production thereof |
EP2616189B1 (en) | 2010-09-14 | 2020-04-01 | Applied NanoStructured Solutions, LLC | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
KR101877475B1 (en) | 2010-09-22 | 2018-07-11 | 어플라이드 나노스트럭처드 솔루션스, 엘엘씨. | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
EP2629595A2 (en) | 2010-09-23 | 2013-08-21 | Applied NanoStructured Solutions, LLC | CNT-infused fiber as a self shielding wire for enhanced power transmission line |
CN102013376B (en) * | 2010-11-29 | 2013-02-13 | 清华大学 | Field emission unit and field emission pixel tube |
US9589580B2 (en) | 2011-03-14 | 2017-03-07 | Cochlear Limited | Sound processing based on a confidence measure |
US8692230B2 (en) | 2011-03-29 | 2014-04-08 | University Of Southern California | High performance field-effect transistors |
US8860137B2 (en) | 2011-06-08 | 2014-10-14 | University Of Southern California | Radio frequency devices based on carbon nanomaterials |
US8699019B2 (en) | 2011-07-13 | 2014-04-15 | OptoTrace (SuZhou) Technologies, Inc. | Assuring food safety using nano-structure based spectral sensing |
US9274105B2 (en) | 2011-07-13 | 2016-03-01 | Optrotrace (SuZhou) Technologies, Inc. | Analyzing chemical and biological substances using nano-structure based spectral sensing |
US9085464B2 (en) | 2012-03-07 | 2015-07-21 | Applied Nanostructured Solutions, Llc | Resistance measurement system and method of using the same |
WO2013158160A1 (en) | 2012-04-16 | 2013-10-24 | Seerstone Llc | Method for producing solid carbon by reducing carbon dioxide |
MX354526B (en) | 2012-04-16 | 2018-03-07 | Seerstone Llc | Methods and systems for capturing and sequestering carbon and for reducing the mass of carbon oxides in a waste gas stream. |
CN104271498B (en) | 2012-04-16 | 2017-10-24 | 赛尔斯通股份有限公司 | The method and structure of oxycarbide is reduced with non-iron catalyst |
WO2013158158A1 (en) | 2012-04-16 | 2013-10-24 | Seerstone Llc | Methods for treating an offgas containing carbon oxides |
NO2749379T3 (en) | 2012-04-16 | 2018-07-28 | ||
US9896341B2 (en) | 2012-04-23 | 2018-02-20 | Seerstone Llc | Methods of forming carbon nanotubes having a bimodal size distribution |
US9604848B2 (en) | 2012-07-12 | 2017-03-28 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
JP6025979B2 (en) | 2012-07-13 | 2016-11-16 | シーアストーン リミテッド ライアビリティ カンパニー | Methods and systems for forming ammonia and solid carbon products |
US9779845B2 (en) | 2012-07-18 | 2017-10-03 | Seerstone Llc | Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same |
US9365426B2 (en) | 2012-07-30 | 2016-06-14 | Scnte, Llc | Process for the production of nanostructured carbon materials |
MX2015006893A (en) | 2012-11-29 | 2016-01-25 | Seerstone Llc | Reactors and methods for producing solid carbon materials. |
EP3113880A4 (en) | 2013-03-15 | 2018-05-16 | Seerstone LLC | Carbon oxide reduction with intermetallic and carbide catalysts |
WO2014150944A1 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Methods of producing hydrogen and solid carbon |
WO2014151138A1 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Reactors, systems, and methods for forming solid products |
EP3129133A4 (en) | 2013-03-15 | 2018-01-10 | Seerstone LLC | Systems for producing solid carbon by reducing carbon oxides |
WO2014151119A2 (en) | 2013-03-15 | 2014-09-25 | Seerstone Llc | Electrodes comprising nanostructured carbon |
KR101445148B1 (en) | 2013-06-04 | 2014-10-01 | 주식회사 이노테라피 | Bioimplantable electrode assembly |
WO2016081787A2 (en) | 2014-11-19 | 2016-05-26 | Biltmore Technologies, Inc. | Controlled color and opacity-changing coating system |
US9379327B1 (en) | 2014-12-16 | 2016-06-28 | Carbonics Inc. | Photolithography based fabrication of 3D structures |
JP2019504290A (en) | 2015-10-07 | 2019-02-14 | ザ・リージェンツ・オブ・ザ・ユニバーシティー・オブ・カリフォルニアThe Regents Of The University Of California | Graphene-based multimodal sensor |
US11752459B2 (en) | 2016-07-28 | 2023-09-12 | Seerstone Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
US10517995B2 (en) | 2016-11-01 | 2019-12-31 | Brigham Young University | Super-hydrophobic materials and associated devices, systems, and methods |
US11471078B1 (en) | 2019-10-30 | 2022-10-18 | Brigham Young University | Miniaturized spectrometers for wearable devices |
US11589764B1 (en) | 2019-10-30 | 2023-02-28 | Brigham Young University | Methods and devices for aligning miniaturized spectrometers and impedance sensors in wearable devices |
US11877845B1 (en) | 2019-10-30 | 2024-01-23 | Brigham Young University | Miniaturized spectrometers on transparent substrates |
US11630316B1 (en) | 2019-10-30 | 2023-04-18 | Brigham Young University | Miniaturized collimators |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2546114B2 (en) | 1992-12-22 | 1996-10-23 | 日本電気株式会社 | Foreign substance-encapsulated carbon nanotubes and method for producing the same |
GB9418937D0 (en) | 1994-09-20 | 1994-11-09 | Isis Innovation | Opening and filling carbon nanotubes |
WO1997019208A1 (en) | 1995-11-22 | 1997-05-29 | Northwestern University | Method of encapsulating a material in a carbon nanotube |
US6129901A (en) | 1997-11-18 | 2000-10-10 | Martin Moskovits | Controlled synthesis and metal-filling of aligned carbon nanotubes |
US6146227A (en) * | 1998-09-28 | 2000-11-14 | Xidex Corporation | Method for manufacturing carbon nanotubes as functional elements of MEMS devices |
-
1999
- 1999-06-14 US US09/333,876 patent/US6361861B2/en not_active Expired - Lifetime
-
2000
- 2000-06-13 WO PCT/US2000/016783 patent/WO2000076912A2/en active Application Filing
- 2000-06-13 AU AU78244/00A patent/AU7824400A/en not_active Abandoned
-
2001
- 2001-11-28 US US09/996,523 patent/US7011771B2/en not_active Expired - Lifetime
Cited By (69)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8487028B2 (en) * | 2000-07-31 | 2013-07-16 | Los Alamos National Security, Llc | Polymer-assisted deposition of films and preparation of carbon nanotube arrays using the films |
US6423583B1 (en) * | 2001-01-03 | 2002-07-23 | International Business Machines Corporation | Methodology for electrically induced selective breakdown of nanotubes |
US20060252276A1 (en) * | 2002-02-09 | 2006-11-09 | Samsung Electronics Co., Ltd. | Method of fabricating memory device utilizing carbon nanotubes |
US7378328B2 (en) * | 2002-02-09 | 2008-05-27 | Samsung Electronics Co., Ltd. | Method of fabricating memory device utilizing carbon nanotubes |
US7039619B2 (en) | 2002-03-12 | 2006-05-02 | Knowm Tech, Llc | Utilized nanotechnology apparatus using a neutral network, a solution and a connection gap |
US7398259B2 (en) | 2002-03-12 | 2008-07-08 | Knowmtech, Llc | Training of a physical neural network |
US20050151615A1 (en) * | 2002-03-12 | 2005-07-14 | Knowmtech, Llc. | Variable resistor apparatus formed utilizing nanotechnology |
US7392230B2 (en) | 2002-03-12 | 2008-06-24 | Knowmtech, Llc | Physical neural network liquid state machine utilizing nanotechnology |
US20050256816A1 (en) * | 2002-03-12 | 2005-11-17 | Knowmtech, Llc. | Solution-based apparatus of an artificial neural network formed utilizing nanotechnology |
US6995649B2 (en) | 2002-03-12 | 2006-02-07 | Knowmtech, Llc | Variable resistor apparatus formed utilizing nanotechnology |
US7107252B2 (en) | 2002-03-12 | 2006-09-12 | Knowm Tech, Llc | Pattern recognition utilizing a nanotechnology-based neural network |
US7028017B2 (en) | 2002-03-12 | 2006-04-11 | Knowm Tech, Llc | Temporal summation device utilizing nanotechnology |
US20050149464A1 (en) * | 2002-03-12 | 2005-07-07 | Knowmtech, Llc. | Pattern recognition utilizing a nanotechnology-based neural network |
US20040153426A1 (en) * | 2002-03-12 | 2004-08-05 | Alex Nugent | Physical neural network liquid state machine utilizing nanotechnology |
US7412428B2 (en) | 2002-03-12 | 2008-08-12 | Knowmtech, Llc. | Application of hebbian and anti-hebbian learning to nanotechnology-based physical neural networks |
US9269043B2 (en) | 2002-03-12 | 2016-02-23 | Knowm Tech, Llc | Memristive neural processor utilizing anti-hebbian and hebbian technology |
US6863852B1 (en) | 2002-05-30 | 2005-03-08 | Zeus Industrial Products, Inc. | Fluoropolymer extrusions based on novel combinations of process parameters and clay minerals |
US20090228415A1 (en) * | 2002-06-05 | 2009-09-10 | Alex Nugent | Multilayer training in a physical neural network formed utilizing nanotechnology |
US7752151B2 (en) | 2002-06-05 | 2010-07-06 | Knowmtech, Llc | Multilayer training in a physical neural network formed utilizing nanotechnology |
US20060141153A1 (en) * | 2002-06-24 | 2006-06-29 | Honda Giken Kogyo Kabushiki Kaisha | Method for making carbon nanotubes |
US20090228416A1 (en) * | 2002-08-22 | 2009-09-10 | Alex Nugent | High density synapse chip using nanoparticles |
US20040039717A1 (en) * | 2002-08-22 | 2004-02-26 | Alex Nugent | High-density synapse chip using nanoparticles |
US7827131B2 (en) | 2002-08-22 | 2010-11-02 | Knowm Tech, Llc | High density synapse chip using nanoparticles |
US8156057B2 (en) | 2003-03-27 | 2012-04-10 | Knowm Tech, Llc | Adaptive neural network utilizing nanotechnology-based components |
US20090043722A1 (en) * | 2003-03-27 | 2009-02-12 | Alex Nugent | Adaptive neural network utilizing nanotechnology-based components |
US20070110971A1 (en) * | 2003-04-17 | 2007-05-17 | Anne-Marie Bonnot | Carbon nanotube growth method |
US8481163B2 (en) * | 2003-04-17 | 2013-07-09 | Centre National De La Recherche Scientifique | Carbon nanotube growth method |
US7426501B2 (en) | 2003-07-18 | 2008-09-16 | Knowntech, Llc | Nanotechnology neural network methods and systems |
EP1528042A1 (en) * | 2003-09-25 | 2005-05-04 | Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. | Method of producing nanostructured magnetic functional elements |
US7341651B2 (en) | 2004-03-22 | 2008-03-11 | The Regents Of The University Of California | Nanoscale mass conveyors |
US20060057767A1 (en) * | 2004-03-22 | 2006-03-16 | Regan Brian C | Nanoscale mass conveyors |
US20100279513A1 (en) * | 2004-04-30 | 2010-11-04 | Nanosys, Inc. | Systems and Methods for Nanowire Growth and Manufacturing |
US20050279274A1 (en) * | 2004-04-30 | 2005-12-22 | Chunming Niu | Systems and methods for nanowire growth and manufacturing |
US7985454B2 (en) | 2004-04-30 | 2011-07-26 | Nanosys, Inc. | Systems and methods for nanowire growth and manufacturing |
US20080197339A1 (en) * | 2004-10-04 | 2008-08-21 | Brian Christopher Regan | Nanocrystal powered nanomotor |
US7863798B2 (en) * | 2004-10-04 | 2011-01-04 | The Regents Of The University Of California | Nanocrystal powered nanomotor |
US9512545B2 (en) * | 2004-11-09 | 2016-12-06 | Board Of Regents, The University Of Texas System | Nanofiber ribbons and sheets and fabrication and application thereof |
US20150147573A1 (en) * | 2004-11-09 | 2015-05-28 | Board Of Regents, The University Of Texas System | Nanofiber ribbons and sheets and fabrication and application thereof |
US10196271B2 (en) | 2004-11-09 | 2019-02-05 | The Board Of Regents, The University Of Texas System | Fabrication and application of nanofiber ribbons and sheets and twisted and non-twisted nanofiber yarns |
US9845554B2 (en) | 2004-11-09 | 2017-12-19 | Board Of Regents, The University Of Texas System | Fabrication and application of nanofiber ribbons and sheets and twisted and non-twisted nanofiber yarns |
US9605363B2 (en) | 2004-11-09 | 2017-03-28 | The Board Of Regents, The University Of Texas System | Fabrication of nanofiber ribbons and sheets |
US7597867B1 (en) | 2004-11-29 | 2009-10-06 | The United States Of America As Represented By The Secretary Of The Navy | Method of carbon nanotube modification |
US7678707B1 (en) | 2004-11-29 | 2010-03-16 | The United States Of America As Represented By The Secretary Of The Navy | Method of carbon nanotube modification |
US7745330B1 (en) | 2004-11-29 | 2010-06-29 | The United States Of America As Represented By The Secretary Of The Navy | Method of carbon nanotube modification |
US20070243717A1 (en) * | 2004-11-29 | 2007-10-18 | Francisco Santiago | Carbon nanotube apparatus and method of carbon nanotube modification |
US7348592B2 (en) | 2004-11-29 | 2008-03-25 | The United States Of America As Represented By The Secretary Of The Navy | Carbon nanotube apparatus and method of carbon nanotube modification |
US20060117797A1 (en) * | 2004-12-08 | 2006-06-08 | Hon Hai Precision Industry Co., Ltd. | Composite mold for molding glass lens |
US7647791B2 (en) * | 2004-12-08 | 2010-01-19 | Hon Hai Precision Industry Co., Ltd. | Composite mold for molding glass lens |
US7502769B2 (en) | 2005-01-31 | 2009-03-10 | Knowmtech, Llc | Fractal memory and computational methods and systems based on nanotechnology |
US7827130B2 (en) | 2005-01-31 | 2010-11-02 | Knowm Tech, Llc | Fractal memory and computational methods and systems based on nanotechnology |
US20060184466A1 (en) * | 2005-01-31 | 2006-08-17 | Alex Nugent | Fractal memory and computational methods and systems based on nanotechnology |
US20090138419A1 (en) * | 2005-01-31 | 2009-05-28 | Alex Nugent | Fractal memory and computational methods and systems based on nanotechnology |
US20070005532A1 (en) * | 2005-05-23 | 2007-01-04 | Alex Nugent | Plasticity-induced self organizing nanotechnology for the extraction of independent components from a data stream |
US7409375B2 (en) | 2005-05-23 | 2008-08-05 | Knowmtech, Llc | Plasticity-induced self organizing nanotechnology for the extraction of independent components from a data stream |
US20070176643A1 (en) * | 2005-06-17 | 2007-08-02 | Alex Nugent | Universal logic gate utilizing nanotechnology |
US7420396B2 (en) | 2005-06-17 | 2008-09-02 | Knowmtech, Llc | Universal logic gate utilizing nanotechnology |
US7599895B2 (en) | 2005-07-07 | 2009-10-06 | Knowm Tech, Llc | Methodology for the configuration and repair of unreliable switching elements |
US20110183139A1 (en) * | 2006-05-01 | 2011-07-28 | Leonid Grigorian | Organized carbon and non-carbon assembly |
US20110145177A1 (en) * | 2007-01-05 | 2011-06-16 | Knowmtech, Llc. | Hierarchical temporal memory |
US8041653B2 (en) | 2007-01-05 | 2011-10-18 | Knowm Tech, Llc | Method and system for a hierarchical temporal memory utilizing a router hierarchy and hebbian and anti-hebbian learning |
US8311958B2 (en) | 2007-01-05 | 2012-11-13 | Knowm Tech, Llc | Hierarchical temporal memory methods and systems |
US7930257B2 (en) | 2007-01-05 | 2011-04-19 | Knowm Tech, Llc | Hierarchical temporal memory utilizing nanotechnology |
US8776870B2 (en) | 2008-05-07 | 2014-07-15 | The Regents Of The University Of California | Tunable thermal link |
US20090277609A1 (en) * | 2008-05-07 | 2009-11-12 | The Regents Of The University Of California | Tunable Thermal Link |
US8623288B1 (en) | 2009-06-29 | 2014-01-07 | Nanosys, Inc. | Apparatus and methods for high density nanowire growth |
US8646745B2 (en) * | 2010-01-22 | 2014-02-11 | Toyota Jidosha Kabushiki Kaisha | Mold, solidified body, and methods of manufacture thereof |
US20110183155A1 (en) * | 2010-01-22 | 2011-07-28 | Toyota Jidosha Kabushiki Kaisha | Mold, solidified body, and methods of manufacture thereof |
US10815124B2 (en) | 2012-07-12 | 2020-10-27 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
WO2019023455A1 (en) * | 2017-07-28 | 2019-01-31 | Seerstone Llc | Solid carbon products comprising carbon nanotubes and methods of forming same |
Also Published As
Publication number | Publication date |
---|---|
US6361861B2 (en) | 2002-03-26 |
WO2000076912A2 (en) | 2000-12-21 |
US20020055010A1 (en) | 2002-05-09 |
AU7824400A (en) | 2001-01-02 |
US7011771B2 (en) | 2006-03-14 |
WO2000076912A3 (en) | 2001-05-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6361861B2 (en) | Carbon nanotubes on a substrate | |
US7157068B2 (en) | Varied morphology carbon nanotubes and method for their manufacture | |
Huczko | Synthesis of aligned carbon nanotubes | |
Ugarte | Morphology and structure of graphitic soot particles generated in arc-discharge C60 production | |
US6582673B1 (en) | Carbon nanotube with a graphitic outer layer: process and application | |
Li et al. | Effect of gas pressure on the growth and structure of carbon nanotubes by chemical vapor deposition | |
Nerushev et al. | Particle size dependence and model for iron-catalyzed growth of carbon nanotubes by thermal chemical vapor deposition | |
Yu et al. | Synthesis of boron nitride nanotubes by means of excimer laser ablation at high temperature | |
Ajayan et al. | Nanometre-size tubes of carbon | |
JP3363759B2 (en) | Carbon nanotube device and method of manufacturing the same | |
Harris | Carbon nanotube science: synthesis, properties and applications | |
Wang et al. | Comparison study of catalyst nanoparticle formation and carbon nanotube growth: support effect | |
Wang et al. | Bamboo-like carbon nanotubes produced by pyrolysis of iron (II) phthalocyanine | |
Mauron et al. | Synthesis of oriented nanotube films by chemical vapor deposition | |
EP1413550B1 (en) | Method and device for synthesizing high orientationally arranged carbon nanotubes by using organic liquid | |
Xie et al. | Carbon nanotube arrays | |
US20060289351A1 (en) | Nanostructures synthesized using anodic aluminum oxide | |
US20110024697A1 (en) | Methods of Producing Carbon Nanotubes and Applications of Same | |
Varadan et al. | Large-scale synthesis of multi-walled carbon nanotubes by microwave CVD | |
Gao et al. | Dense arrays of well-aligned carbon nanotubes completely filled with single crystalline titanium carbide wires on titanium substrates | |
Govindaraj et al. | Organometallic precursor route to carbon nanotubes | |
JP3453378B2 (en) | Radial aggregate of sharp-end multi-walled carbon nanotubes and method for producing the same | |
Täschner et al. | Synthesis of aligned carbon nanotubes by DC plasma-enhanced hot filament CVD | |
TW201420499A (en) | Carbon nanotubes conformally coated with diamond nanocrystals or silicon carbide, methods of making the same and methods of their use | |
Kim et al. | Synthesis of high-density carbon nanotube films by microwave plasma chemical vapor deposition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BATTELLE MEMORIAL INSTITUTE K1-53, WASHINGTON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GAO, YUFEI;LIU, JUN;REEL/FRAME:010219/0698;SIGNING DATES FROM 19990614 TO 19990623 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
AS | Assignment |
Owner name: U.S. DEPARTMENT OF ENERGY, DISTRICT OF COLUMBIA Free format text: CONFIRMATORY LICENSE;ASSIGNOR:BATTELLE MEMORIAL INSTITUTE, PACIFIC NORTHWEST DIVISION;REEL/FRAME:014301/0481 Effective date: 19990830 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |