US20120177808A1 - System and method for low-power nanotube growth using direct resistive heating - Google Patents
System and method for low-power nanotube growth using direct resistive heating Download PDFInfo
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- US20120177808A1 US20120177808A1 US12/102,302 US10230208A US2012177808A1 US 20120177808 A1 US20120177808 A1 US 20120177808A1 US 10230208 A US10230208 A US 10230208A US 2012177808 A1 US2012177808 A1 US 2012177808A1
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- 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
- Y10S977/813—Of specified inorganic semiconductor composition, e.g. periodic table group IV-VI compositions
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- 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
- Y10S977/813—Of specified inorganic semiconductor composition, e.g. periodic table group IV-VI compositions
- Y10S977/814—Group IV based elements and compounds, e.g. CxSiyGez, porous silicon
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- 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
- Y10S977/813—Of specified inorganic semiconductor composition, e.g. periodic table group IV-VI compositions
- Y10S977/815—Group III-V based compounds, e.g. AlaGabIncNxPyAsz
- Y10S977/822—Boron-containing compounds
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- 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
- Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10T117/10—Apparatus
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- 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
- Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10T117/10—Apparatus
- Y10T117/1016—Apparatus with means for treating single-crystal [e.g., heat treating]
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- 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
- Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
- Y10T117/10—Apparatus
- Y10T117/102—Apparatus for forming a platelet shape or a small diameter, elongate, generally cylindrical shape [e.g., whisker, fiber, needle, filament]
Definitions
- This invention relates to nanotube (NT) growth of Carbon and other materials such as Germanium, Boron, Boron-Nitride, Boron-Carbide, B i C j N k , Silica and Silica-Carbide, and more particular to a low-power approach to growing nanotubes.
- Carbon nanotubes have stimulated a great deal of interest in the microelectronic and other industries because of their unique properties including tensile strengths above 35 GPa, elastic modulus reaching 1 TPa, higher thermal conductivity than diamond, ability to carry 1000 ⁇ the current of copper, densities below 1.3 g/cm 3 and high chemical, thermal and radiation stability. CNTs have great promise for devices such as field effect transistors, field emission displays, single electron transistors in the microelectronic industry, and uses in other industries. Commercialization of CNTs will depend in large part on the ability to grow and network CNTs on a large cost-effective scale without compromising these properties.
- a CNT 10 is a hollow cylindrical shaped carbon molecule.
- the cylinderical structure is built from a hexagonal lattice of sp 2 bonded carbon atoms 12 with no dangling bonds.
- the properties of single-walled nanotubes (SWNTs) are determined by the graphene structure in which the carbon atoms are arranged to form the cylinder.
- Multi-walled nanotubes (MWNTs) are made of concentric cylinders around a common central hollow.
- CNTs are commonly grown using several techniques such as arc discharge, laser ablation and chemical vapour deposition (CVD).
- CVD the growth of a CNT is determined by the presence of a catalyst, usually a transition metal such as Fe, Co or Ni, which causes the catalytic dehydrogenation of hydrocarbons and consequently the formation of a CNT.
- a catalyst usually a transition metal such as Fe, Co or Ni, which causes the catalytic dehydrogenation of hydrocarbons and consequently the formation of a CNT.
- CVD generally produces MWNTs or SWNTs of relatively poor quality due mostly to the poorly controlled diameters of the nanotubes.
- CVD is relatively easy to scale up and can be integrated with conventional microelectronic fabrication, which favors commercialization.
- a catalyst 20 is deposited on a support such as silicon, zeolite, quartz, or inconel 22 .
- a carbon containing gas causes the catalyst to take in carbon, on either the surfaces, into the bulk, or both.
- This thermal diffusion process of neutral carbon atoms occurs at energies of a few electronvolts (eV).
- a precursor to the formation of nanotubes and fullerenes, C 2 is formed on the surface of the catalyst.
- a rodlike carbon 24 is formed rapidly, followed by a slow graphitization of its wall.
- the CNT can form either by ‘extrusion’ (also know as ‘base growth’ or ‘root growth’) shown in FIG. 2 a , in which the CNT grows upwards from the catalyst that remains attached to the support, or the particles can detach from the substrate and move at the head of the growing nanotube, labelled ‘tip-growth’, as shown in FIG. 2 b .
- SWNT or MWNT are grown.
- a typical catalyst may contain an alloy of Fe, Co or Ni atoms having a total diameter of 1 to 100 nm (on the order of 1,000 atoms for 1 nm diameter of catalyst).
- thermal energy or heat is essential to stimulate the growth mechanism of CNTs.
- Heat is required to break the hydrocarbon molecules in the carbon containing gas upon colliding with the catalyst so they attach to the catalysts. Heat is required to transport these carbon atoms via diffussion processes to the interface of the catalyst and the carbon nanotubes to obtain higher growth rates. Heat is required for the CNT to attach the carbon atoms quickly for fast growth.
- the thermal energy must be controlled to provide sufficient heating to stimulate these growth processes without melting the catalyst of breaking the CNT. Typically heating is provided by induction, plasma discharge, substrate or wall heating. The power consumption required by these methods of indirect heating of the catalyst is a significant factor in the manufacturing cost.
- the support 22 and catalytic material 20 are placed inside an environmentally-controlled chamber 32 .
- the sample is heated until the temperature is great enough (400° C.) that the introduction of hydrogen along with a buffer gas (Argon) “reduces” (removes the oxide) the particle.
- a buffer gas Aron
- a plurality of gas feeds 34 introduce a process gas including a mixture of a carbon-containing growth gas 36 , typically a hydrocarbon C x H y such as Ethylene (C 2 H 4 ), Methane (CH 4 ), Ethanol (C 2 H 5 OH), or Acetylene (C 2 H 2 ) or possibly a non-hydrocarbon such as carbon-monoxide (CO), an inert buffer gas 38 such as Argon (Ar) to control pressure inside the chamber and prevent released hydrogen atoms from exploding and possibly a scrubber gas 40 such as H 2 O or O 2 to periodically or continuously clean the surface of the catalyst.
- An energy source 42 such as induction, plasma discharge, substrate or wall heating provides the energy necessary (e.g.
- a pump system 46 including a vacuum and/or pressure pump controls the pressure inside the chamber to produce conditions both conducive to absorption of carbon atoms into the catalytic material and growth of CNTs from the catalytic material.
- a number of electrical ports 48 are provided to accommodate pressure sensors, thermocouples and the like to monitor conditions inside the chamber.
- CVD can be used to synthesize an array of vertically aligned CNTs 50 between a Si substrate 52 and a metal thin-film 54 , suitably nickel, via a lift-off process.
- the thin-film is formed over Fe particles 56 on substrate 52 that serve as catalysts.
- the CVD process initiates nanotube growth that ‘lifts’ thin-film 54 off of the substrate.
- the fabrication of three-dimensional networks of CNTs with controlled orientation will be essential for building large-scale function devices integrated with microelectronics circuits. Bingqing Wei et al.
- the present invention provides a low-power system and method for growing nanotubes out of carbon and other materials using a CVD, ion implantation or hybrid process with direct resistive heating of the nanotubes.
- An electrical source is connected between the substrate and a plate over the nanotubes to cause electrical current to flow through and resistively heat the nanotubes and their catalysts.
- the process of nanotube growth continues using a CVD or ion implantation process through completion.
- the direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used thereby improving heating efficiency and reducing overall power consumption.
- a sensed condition indicative of the temperature of the nanotubes is suitably fed back to control the electrical source to maintain a temperature within a desired range for optimal growth.
- opposite ends of the nanotubes are physically bonded to the substrate and the plate.
- the electrical source is a current source that supplies the electrical current to the nanotubes.
- the plate may be lifted by the growth of nanotubes.
- a mechanical actuator can lift the plate. The actuator can be controlled to either match the growth rate or to exert a small pulling force on the nanotubes to increase the growth rate. If the nanotubes exhibit the same chirality they should grow at the same rate. Statistically some nanotubes will grow slower than others. Those nanotubes will exhibit a lower resistance and thus draw a higher proportion of the sourced current. This additional heating should further stimulate growth to keep the growth rate of the entire array fairly uniform. If the nanotubes exhibit different chiralities they will grow at different rates. The bonds of the slower growing nanotubes will likely break thereby producing an array of only nanotubes having one chirality with the fastest growth rate.
- a mechanical actuator maintains the plate at a small distance above the nanotubes.
- the electrical source is a voltage source, whereby application of a voltage across the gap between the free end of the nanotubes and the plate causes field emission to occur and electrical current to flow through the nanotubes. If the nanotubes exhibit the same chirality they should grow at the same rate. If the nanotubes exhibit different chiralities some of them will grow slower than the others.
- the actuator maintains the distance to the tallest fastest growing nanotubes. This increases the gap to the shorter nanotubes which reduces the amount of current to those nanotubes further slowing their growth. This approach can be used to filter the nanotubes by chirality, particularly the fastest growing nanotubes.
- the actuator may contact the plate to the tallest nanotubes in an oxygen environment to burn up the nanotubes. The actuator then maintains the plate at a distance above another subset of nanotubes having a chirality that exhibits the highest growth rate among the remaining nanotubes.
- a conventional hot CVD process is used to form the growth-initiated array of nanotubes. Once direct resistive heating of the nanotubes is initiated the CVD process is run cold to improve energy efficiency.
- the CVD process can be configured with a single feedstock/growth chamber as per convention or the substrate can be used to separate the chamber into a feedstock chamber on one side and a growth chamber on the other. The latter approach separates nanotube growth from the noxious feedstock gases which tend to deteriorate the catalyst with byproducts over time.
- an ion implantation process is used to form the growth-initiated array of nanotubes.
- the requisite heating can be provided indirectly by wall or substrate heating or by the energy in the ion beam itself. Once direct resistive heating of the nanotubes is initiated the indirect heat source can be removed or reduced (reduced beam energy) to improve energy efficiency.
- the ion implantation process can be configured with a single implantation/growth chamber or the substrate can be configured to provide an implantation region on one side and a growth region on the other. The two chambers may be held in the same vacuum or the substrate may provide an environmental seal for independent control. This approach separates nanotube growth from the ion beam.
- a hybrid CVD and ion implantation process is used.
- the substrate forms a seal creating two separate chambers.
- a feedstock/growth chamber is formed on one side of the substrate and an implantation chamber on the other side of the substrate.
- a CVD process initiates growth of the nanotube array. Current is passed through the nanotubes to provide the direct resistive heating. At this point, either the CVD process can be run cold for awhile before switching to the ion implantation process or the ion implantation process can start immediately.
- the hybrid approach combines the fast growth capability of the CVD process to initiate growth with the sustained growth capability of ion implantation to grow nanotubes of arbitrary length.
- FIG. 1 is a diagram of a carbon nanotube
- FIGS. 2 a - 2 b are diagrams illustrating root and tip CNT growth
- FIG. 3 is a diagram of a conventional CVD process using a single feedstock-growth chamber to grow CNTs on a substrate;
- FIGS. 4 a and 4 b are diagrams of a CVD “lift-off” process for growing an array of CNTs that lifts a metal thin-film;
- FIGS. 5 a and 5 b are physical and electrical schematic diagrams of a current source connected across a growth-initiated CNT array to provide direct resistive heating of the nanotubes and their respective catalysts;
- FIGS. 6 a through 6 c are diagrams of carbon nanotubes illustrating armchair, zig-zag and chiral orientations, respectively;
- FIGS. 7 a and 7 b are diagrams of a voltage source connected between a growth-initiated CNT array and a plate to stimulate field emission to provide direct resistive heating of the nanotubes and their catalysts for single and multiple chirality growth, respectively;
- FIG. 8 is a diagram of a feedstock/growth chamber for a low-power CVD process
- FIG. 9 is a diagram of a low-power CVD process in which the substrate separates the feedstock and growth chambers;
- FIG. 10 is a diagram of an implantation/growth chamber for a low-power ion implantation process
- FIG. 11 is a diagram of a low-power ion implantation process in which the substrate separates implantation and growth regions;
- FIG. 12 is a diagram of a low-power hybrid CVD-ion implantation process in which the substrates isolates an implantation chamber from a feedstock/growth chamber;
- FIG. 13 is a diagram of a single nanotube in which a second catalyst has been formed within the nanotube.
- the present invention provides a low-power system and method for growing nanotubes out of carbon and other materials such as Germanium, Boron, Boron-Nitride, Boron-Carbide, B i C j N k where i, j and k are any non-negative integers, Silicon and Silicon-Carbide using a CVD, ion implantation or hybrid process with direct resistive heating of the nanotubes.
- This is accomplished by providing a growth-initiated array of nanotubes.
- An electrical source is connected between the substrate and a plate over the nanotubes (in contact with or separated by a small gap) to cause electrical current to flow through the nanotubes producing direct resistive heating of the nanotubes and their catalysts.
- the process of nanotube growth continues using a CVD or ion implantation process through completion.
- the direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used thereby improving heating efficiency and reducing overall power consumption.
- a sensed condition indicative of the temperature of the nanotubes is suitably fed back to control the electrical source to maintain a temperature within a desired range for optimal growth.
- some process such as CVD or ion implantation is used to provide a growth-initiated array of nanotubes 60 in which the nanotubes and their respective catalysts 62 are supported between and bonded to a substrate 64 and a plate 66 .
- Plate 66 is suitably a metal thin-film such as nickel provided via a lift-off process.
- the nanotubes are grown via lip growth'.
- the nanotubes may be alternately grown via ‘root growth’ or both.
- Either growth process uses some type of indirect heating to heat the catalysts to initiate nanotube growth. Indirect heating is an inefficient approach to heating the catalysts because much energy is expended to heat the environment inside the chamber, substrate, chamber walls etc. However, it is needed to initiate nanotube growth.
- a current source 68 is connected across the substrate 64 and thin-film 66 , which are configured to provide electrical contacts at opposite ends of the nanotubes, to close an electrical circuit.
- the substrate and thin-film typically conduct electrical current. Alternately, conductive traces or paths could be formed in either or both if non-conductive.
- the current source sources electrical current i S 70 that flows through the nanotubes as i NT 72 producing direct resistive heating 74 of the nanotubes and their catalysts (and the nearby surrounding gas in a CVD process).
- a controller 76 suitably controls the amount of current i S 70 to maintain the nanotube temperature in a desired range for optimal growth. Typical ranges for carbon nanotube growth are 400 to 1000 degrees Celsius.
- the initial current is set based on a calculation or empirical evidence of the estimated number of nanotubes and average resistance.
- the control may operate open-loop depending on the temperature tolerances.
- one or more sensors 78 suitably sense a condition indicative of the temperature of the nanotubes that is fed back to the controller 76 to control the current source to maintain the temperature within the desired range.
- the sensed condition may be the temperature of the nanotubes or another parameter correlated to temperature.
- an optical pyrometer outside the chamber is used to directly sense the temperature inside the chamber.
- An optical pyrometer generally senses the maximum temperature in an imaged area. The thin-film may be lifted by the growth of nanotubes.
- a mechanical actuator 80 such as a piezo actuator can lift the thin-film 66 .
- the actuator can be controlled to either match the growth rate or to exert a small pulling force on the nanotubes to place them under tensile stress and increase the growth rate.
- the process of nanotube growth continues using a growth process such as CVD or ion implantation through completion.
- the direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used thereby improving heating efficiency and reducing overall power consumption.
- the carbon nanotubes 60 grow as a hollow cylindrical shaped carbon molecule built from a hexagonal lattice of sp 2 bonded carbon atoms with no dangling bonds.
- the orientation of the hexagonal lattice can exhibit different ‘chirality’ e.g. armchair 82 , zig-zag 84 , and chiral 86 .
- the different chiralities exhibit different electrical and thermal conductivities and different growth rates.
- the array of carbon nanotubes will exhibit different chiralities somewhat randomly across the array.
- a process such as CVD or ion implantation is used to provide a growth-initiated array of nanotubes 90 in which the nanotubes 90 and their respective catalysts 92 are supported on a substrate 94 .
- the nanotubes are grown via ‘root growth’.
- the nanotubes may be alternately grown via ‘tip growth’ or both.
- Either growth process uses some type of indirect heating to heat the catalysts to initiate nanotube growth. Indirect heating is an inefficient approach to heating the catalysts because much energy is expended to heat the environment inside the chamber, substrate, chamber walls etc. However, it is needed to initiate nanotube growth.
- a mechanical actuator 96 maintains a plate 98 at a small distance above the nanotubes.
- a voltage source 100 connected across the substrate 94 and plate 98 applies a voltage across a gap 102 between the free end 104 of the nanotubes 90 and the plate 98 causing field emission of electrons 106 to occur and electrical current i NT 108 to flow through the nanotubes 90 producing direct resistive heating 110 of the nanotubes and their catalysts (and the surrounding gas in a CVD process).
- a controller 112 controls the voltage level and/or the actuator 96 controls the gap to adjust the current level to maintain the nanotube temperature in a desired range for optimal growth.
- the initial voltage is set based on a calculation or empirical evidence of the estimated number of nanotubes and average resistance.
- the controller may simply fix the voltage level or vary it based on calculations or empirical evidence.
- one or more sensors 114 suitably sense a condition indicative of the temperature of the nanotubes, which is fed back to the controller 112 to control the voltage source and/or mechanical actuator to maintain the temperature within the desired range.
- the sensed condition may be the temperature of the nanotubes or another parameter correlated to temperature.
- the process of nanotube growth continues using a CVD or ion implantation process through completion.
- the direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used to improve heating efficiency and reduce overall power consumption.
- the carbon nanotubes may exhibit different chiralities. If, as depicted in FIG. 7 a , the nanotubes 90 exhibit the same chirality they should grow at the same rate. If, as depicted in FIG. 7 b , the nanotubes 90 exhibit different chiralities some of them will grow slower than the others.
- the actuator 96 maintains the distance to the tallest fastest growing nanotubes. This increases the gap to the shorter nanotubes which reduces the amount of current to those nanotubes further slowing their growth. If the gap is large enough field emission, hence current flow will cease. This approach can be used to filter the nanotubes by chirality, particularly the fastest growing nanotubes.
- oxygen gas 116 is fed into the chamber via line 118 and the actuator contacts the plate to the tallest nanotubes to burn up the nanotubes.
- the oxygen is pumped out of the chamber and actuator then maintains the plate at a distance above another subset of nanotubes having a chirality that exhibits the highest growth rate among the remaining nanotubes.
- Direct resistive heating to grow nanotubes out of carbon and other materials can be implemented with, for example, CVD, ion implantation or hybrid growth processes. Both the current and voltage source embodiments can be used with any of these or other growth processes. By way of example only, each of these growth processes will be described in context of the current source embodiment.
- a conventional hot CVD process can be used to form the growth-initiated array of nanotubes. Once direct resistive heating of the nanotubes is initiated the CVD process is run cold to improve energy efficiency.
- the CVD process can be configured with a single feedstock/growth chamber as per convention ( FIG. 8 ) or the substrate can be configured with catalyst material embedded therein that provides a feedstock chamber on one side and a growth chamber on the other ( FIG. 9 ).
- the latter approach separates nanotube growth from the noxious feedstock gases.
- the latter approach is detailed in co-pending U.S. application Ser. No. 11/969,533 entitled “Carbon Nanotube Growth via Chemical Vapor Deposition using a Catalytic Transmembrane to Separate Feedstock and Growth Chambers” filed on Jan. 4, 2008, the contents of which are incorporated by reference.
- a plurality of gas feeds 134 introduce a process gas including a mixture of a carbon-containing growth gas 136 , typically a hydrocarbon C x H y such as Ethylene (C 2 H 4 ), Methane (CH 4 ), Ethanol (C 2 H 5 OH), or Acetylene (C 2 H 2 ) or possibly a non-hydrocarbon such as carbon-monoxide (CO), an inert buffer gas 138 such Argon (Ar) to control pressure inside the chamber and prevent released hydrogen atoms from exploding and possibly a scrubber gas 140 such as H 2 O or O 2 to periodically or continuously clean the surface of the catalyst.
- a carbon-containing growth gas 136 typically a hydrocarbon C x H y such as Ethylene (C 2 H 4 ), Methane (CH 4 ), Ethanol (C 2 H 5 OH), or Acetylene (C 2 H 2 ) or possibly a non-hydrocarbon such as carbon-monoxide (CO)
- An energy source 142 such as induction, plasma discharge, substrate or wall heating provides the energy necessary (e.g. a few eV) for a hot CVD process to heat the catalyst to a temperature which allows it to ‘crack’ the hydrocarbon molecules into reactive atomic carbon 144 , to heat the catalyst to increase the transport of carbon to the catalysts/CNT interface and to heat the CNT itself.
- the reactive carbon 144 is absorbed into the surface of catalyst 120 causing the CNT 124 to grow from the same catalytic surface and lift-thin film 126 .
- a pump system 146 including a vacuum and/or pressure pump controls the pressure inside the chamber to produce conditions both conducive to absorption of carbon atoms into the catalytic material and growth of CNTs from the catalytic material.
- a number of ports 148 are provided to accommodate pressure sensors, thermocouples and the like to monitor conditions inside the chamber.
- a direct resistive heating system includes a current source 150 that is electrically connected through ports 148 between substrate 122 and thin-film 126 to source current through the parallel-combination of nanotubes 124 , a temperature sensor 152 such as an optical pyrometer that that senses the temperature of the nanotubes through a port 148 and a controller 154 that processes the temperature data to adjust the total source current to maintain the temperature in a desired range for optimal nanotube growth.
- energy source 142 is suitably turned off and the heat required to crack the hydrocarbon molecules colliding with the catalyst, heat the catalyst for more rapid diffussion and to heat the CNT is provided by the direct resistive heating 156 .
- the energy and power required to operate the current source is far less than the energy required to operate indirect energy source 142 .
- direct resistive heating can also be used in conjunction with a modified CVD process in which the substrate 122 is secured by a gasket 160 to separate the chamber into a feedstock chamber 162 and a growth chamber 164 in which the growth-gas is confined to the feedstock chamber.
- the catalysts 120 are embedded in the substrate with portions 166 of catalyst surface exposed to the feedstock chamber for absorbing carbon atoms 144 from the growth gas and different portions of catalyst surface 168 exposed to the growth chamber to grow nanotubes 124 in an environment devoid of said growth gas.
- a vacuum or pressure pump 170 controls the pressure in the growth chamber.
- a buffer gas 172 may be fed into the chamber through lines 174 if desired.
- Substrate 122 is suitably quite thin, a few millimeters thick. Consequently the direct heating of the CNTs and catalysts in the growth chamber efficiently heats the gases in the feed stock chamber providing sufficient energy to ‘crack’ the hydrocarbon molecules which come into contact with the hot tubes and catalysts.
- An ion implantation process can be used to form the growth-initiated array of nanotubes. Once direct resistive heating of the nanotubes is initiated the indirect heat source used to initiate growth is turned off or at least reduced to improve overall energy efficiency.
- the ion implantation process can be configured with a single implantation/growth chamber ( FIG. 10 ) or the substrate can be configured with catalyst material embedded therein or thereon that provides an implantation region on one side and a growth region on the other ( FIG. 11 ). The latter approach separates nanotube growth from the ion beam.
- the ion implantation approach is detailed in co-pending U.S. application Ser. No.
- a substrate 200 having one or more catalysts 202 supported thereon and covered by a thin-film 204 is placed inside an environmentally controlled chamber 206 held at vacuum by a vacuum pump 207 .
- a source 208 directs a beam of carbon ions 210 through the thin-film to implant the ions into the catalysts 202 .
- the energy of the ion beam itself or an indirect energy source 212 provides the thermal energy necessary to heat the catalysts for proper diffussion and attachment of carbon atoms to initiate growth of CNTs 214 .
- a direct resistive heating system includes a current source 220 that is electrically connected through ports 222 between substrate 200 and thin-film 204 to source current through the parallel-combination of nanotubes 214 , a temperature sensor 224 such as an optical pyrometer that that senses the temperature of the nanotubes through a port 222 and a controller 226 that processes the temperature data to adjust the total source current to maintain the temperature in a desired range for optimal nanotube growth.
- energy source 212 is suitably turned off or reduced (e.g. if ion beam provides heating, reduce beam energy) and the heat required to heat the catalyst for more rapid diffussion and to heat the CNT is provided by the direct resistive heating 228 .
- the energy and power required to operate the current source 220 is far less than the energy required to operate indirect energy source 212 and/or to operate the ion beam at higher energy levels.
- direct resistive heating can also be used in conjunction with a modified ion implant process in which substrate 200 physically separates chamber 206 into an implantation region 230 and a growth region 232 .
- Catalysts 202 supported on the underside of substrate 200 (or embedded in the substrate) provide an implantation surface 234 to receive carbon ions from beam 210 with sufficient energy to reach, penetrate and stop in the catalyst and a growth surface 236 directly exposed to the growth region to grow carbon nanotubes 214 .
- This configuration protects the CNTs from the ion beam.
- “knock-on” processes can be used to increase the flux of carbon ions implanted into the catalysts.
- a spacer layer 240 separates a knock on layer 242 (e.g.
- Graphite from the catalyst material.
- An anti-sputtering layer 244 e.g. Ti, Mo, etc.
- Source 208 directs ion beam 210 through the anti-sputtering layer onto knock-on layer 242 .
- knock-on Through a “knock-on” process, each ion knocks multiple carbon ions forward through the substrate into catalyst 202 thereby providing gain.
- the source does not have to emit carbon ions, it could, for example, emit heavier ions to improve knock-on efficiency.
- a gasket is fitted around substrate 200 to isolate an implantation chamber from a growth chamber. Consequently, the pressure and gas environment of the growth chamber can be independently controlled as desired.
- Direct resistive heating can be similarly used in a hybrid CVD/ion implantation process.
- the substrate forms a seal creating two separate chambers.
- a feedstock/growth chamber is formed on one side of the substrate and an implantation chamber on the other side of the substrate.
- a CVD process initiates growth of the nanotube array. Current is passed through the nanotubes to provide the direct resistive heating. At this point, either the CVD process can be run cold for awhile before switching to the ion implantation process or the ion implantation process can start immediately.
- the hybrid approach combines the fast growth capability of the CVD process to initiate growth with the sustained growth capability of ion implantation to grow nanotubes of arbitrary length.
- a substrate 300 with one or more catalysts 302 on the underside of the substrate or embedded therein and with a thin-film 304 over the catalysts is placed inside an environmentally controlled chamber 306 .
- a gasket 308 holds the substrate 300 to form a seal that separates the chamber into a feedstock and growth chamber 310 for CVD and an implantation chamber 312 for ion implantation.
- a plurality of gas feeds 314 introduce a process gas including a mixture of a carbon-containing growth gas 316 , typically a hydrocarbon C x H y such as Ethylene (C 2 H 4 ), Methane (CH 4 ), Ethanol (C 2 H 5 OH), or Acetylene (C 2 H 2 ) or possibly a non-hydrocarbon such as carbon-monoxide (CO), an inert buffer gas 318 such Argon (Ar) to control pressure inside the chamber and prevent released hydrogen atoms from exploding and possibly a scrubber gas 320 such as H 2 O or O 2 to periodically or continuously clean the surface of the catalyst.
- An energy source 322 such as induction, plasma discharge, substrate or wall heating provides the energy necessary (e.g.
- a pump system 326 including a vacuum and/or pressure pump controls the pressure inside the chamber to produce conditions both conducive to absorption of carbon atoms into the catalyst and growth of CNTs from the catalyst.
- a direct resistive heating system includes a current source 330 that is electrically connected through ports 332 between substrate 300 and thin-film 304 to source current through the parallel-combination of nanotubes 324 , a temperature sensor 334 such as an optical pyrometer that that senses the temperature of the nanotubes through a port 332 and a controller 336 that processes the temperature data to adjust the total source current to maintain the temperature in a desired range for optimal nanotube growth.
- energy source 332 is suitably turned off and the heat required to heat the catalyst for more rapid diffussion and to heat the CNT is provided by the direct resistive heating 338 .
- a vacuum pump 340 holds the implantation chamber 312 at vacuum.
- a source 342 directs a beam of ions 344 towards the substrate to cause carbon ions 346 to be implanted into catalyst 302 .
- the beam may inject carbon ions directly into the catalysts or amplify them, as shown, using ‘knock-on’ processes.
- a spacer layer 348 separates a knock on layer 350 (e.g. Graphite) from the catalyst material.
- An anti-sputtering layer 352 (e.g. Ti, Mo, etc.) is deposited over the knock-on layer.
- Source 342 directs ion beam 244 through the anti-sputtering layer onto knock-on layer 350 . Through a “knock-on” process, each ion knocks multiple carbon ions forward through the substrate into catalyst 302 thereby providing gain.
- Direct resistive heating is used to effectively and energy efficiently grow one or more nanotubes.
- nanotube growth can be further stimulated by the formation of additional catalysts within the nanotubes as they grow.
- root growth of a catalyst 400 on substrate 402 produces a nanotube 404 .
- An element-containing gas or mist 406 for example, is introduced into the chamber environment through a gas feed 408 .
- An electron beam 410 bombards the nanotubes in the element-containing environment to form an additional catalyst 412 at the tip of the growing nanotubes.
- the tip is attached to a thin-film 414 to support the direct resistive heating.
- the tip may be unattached.
- the additional catalyst 412 may grow the nanotube via root or tip growth. The process can be repeated for another catalyst 414 on the free end of the nanotube.
- This process for forming additional catalysts within the nanotubes to further stimulate and speed growth is not limited to direct resistive heating, the process can be used in any of the CVD or ion implantation processes with or without direct resistive heating.
Abstract
Description
- 1. Field of the Invention
- This invention relates to nanotube (NT) growth of Carbon and other materials such as Germanium, Boron, Boron-Nitride, Boron-Carbide, BiCjNk, Silica and Silica-Carbide, and more particular to a low-power approach to growing nanotubes.
- 2. Description of the Related Art
- Carbon nanotubes (CNTs) have stimulated a great deal of interest in the microelectronic and other industries because of their unique properties including tensile strengths above 35 GPa, elastic modulus reaching 1 TPa, higher thermal conductivity than diamond, ability to carry 1000× the current of copper, densities below 1.3 g/cm3 and high chemical, thermal and radiation stability. CNTs have great promise for devices such as field effect transistors, field emission displays, single electron transistors in the microelectronic industry, and uses in other industries. Commercialization of CNTs will depend in large part on the ability to grow and network CNTs on a large cost-effective scale without compromising these properties.
- As illustrated in
FIG. 1 , aCNT 10 is a hollow cylindrical shaped carbon molecule. The cylinderical structure is built from a hexagonal lattice of sp2bonded carbon atoms 12 with no dangling bonds. The properties of single-walled nanotubes (SWNTs) are determined by the graphene structure in which the carbon atoms are arranged to form the cylinder. Multi-walled nanotubes (MWNTs) are made of concentric cylinders around a common central hollow. - CNTs are commonly grown using several techniques such as arc discharge, laser ablation and chemical vapour deposition (CVD). In CVD the growth ofa CNT is determined by the presence of a catalyst, usually a transition metal such as Fe, Co or Ni, which causes the catalytic dehydrogenation of hydrocarbons and consequently the formation of a CNT. CVD generally produces MWNTs or SWNTs of relatively poor quality due mostly to the poorly controlled diameters of the nanotubes. However, CVD is relatively easy to scale up and can be integrated with conventional microelectronic fabrication, which favors commercialization.
- The way in which nanotubes are formed at the atomic scale is not precisely known. The growth mechanism is still a subject of scientific debate, and more than one mechanism might be operative during the formation of CNTs. As shown in
FIGS. 2 a and 2 b, acatalyst 20 is deposited on a support such as silicon, zeolite, quartz, orinconel 22. At elevated temperatures, exposure to a carbon containing gas causes the catalyst to take in carbon, on either the surfaces, into the bulk, or both. This thermal diffusion process of neutral carbon atoms occurs at energies of a few electronvolts (eV). A precursor to the formation of nanotubes and fullerenes, C2, is formed on the surface of the catalyst. From this precursor, arodlike carbon 24 is formed rapidly, followed by a slow graphitization of its wall. The CNT can form either by ‘extrusion’ (also know as ‘base growth’ or ‘root growth’) shown inFIG. 2 a, in which the CNT grows upwards from the catalyst that remains attached to the support, or the particles can detach from the substrate and move at the head of the growing nanotube, labelled ‘tip-growth’, as shown inFIG. 2 b. Depending on the size of the catalyst particle either SWNT or MWNT are grown. A typical catalyst may contain an alloy of Fe, Co or Ni atoms having a total diameter of 1 to 100 nm (on the order of 1,000 atoms for 1 nm diameter of catalyst). - The application of thermal energy or heat is essential to stimulate the growth mechanism of CNTs. Heat is required to break the hydrocarbon molecules in the carbon containing gas upon colliding with the catalyst so they attach to the catalysts. Heat is required to transport these carbon atoms via diffussion processes to the interface of the catalyst and the carbon nanotubes to obtain higher growth rates. Heat is required for the CNT to attach the carbon atoms quickly for fast growth. The thermal energy must be controlled to provide sufficient heating to stimulate these growth processes without melting the catalyst of breaking the CNT. Typically heating is provided by induction, plasma discharge, substrate or wall heating. The power consumption required by these methods of indirect heating of the catalyst is a significant factor in the manufacturing cost.
- As shown in
FIG. 3 , to synthesizeCNTs 24 using CVD thesupport 22 andcatalytic material 20 are placed inside an environmentally-controlledchamber 32. The sample is heated until the temperature is great enough (400° C.) that the introduction of hydrogen along with a buffer gas (Argon) “reduces” (removes the oxide) the particle. A plurality ofgas feeds 34 introduce a process gas including a mixture of a carbon-containinggrowth gas 36, typically a hydrocarbon CxHy such as Ethylene (C2H4), Methane (CH4), Ethanol (C2H5OH), or Acetylene (C2H2) or possibly a non-hydrocarbon such as carbon-monoxide (CO), aninert buffer gas 38 such as Argon (Ar) to control pressure inside the chamber and prevent released hydrogen atoms from exploding and possibly ascrubber gas 40 such as H2O or O2 to periodically or continuously clean the surface of the catalyst. Anenergy source 42 such as induction, plasma discharge, substrate or wall heating provides the energy necessary (e.g. a few eV) to heat the catalyst to a temperature which allows it to ‘crack’ the hydrocarbon molecules into reactiveatomic carbon 44 upon colliding with the catalyst, to heat the catalyst to increase the transport of carbon to the catalysts/CNT interface and to heat the CNT itself. Thereactive carbon 44 is absorbed into the surface ofcatalytic material 20 causing the CNT to grow from the same catalytic surface. Apump system 46 including a vacuum and/or pressure pump controls the pressure inside the chamber to produce conditions both conducive to absorption of carbon atoms into the catalytic material and growth of CNTs from the catalytic material. A number ofelectrical ports 48 are provided to accommodate pressure sensors, thermocouples and the like to monitor conditions inside the chamber. - As shown in
FIGS. 4 a and 4 b, CVD can be used to synthesize an array of vertically alignedCNTs 50 between aSi substrate 52 and a metal thin-film 54, suitably nickel, via a lift-off process. The thin-film is formed overFe particles 56 onsubstrate 52 that serve as catalysts. The CVD process initiates nanotube growth that ‘lifts’ thin-film 54 off of the substrate. The fabrication of three-dimensional networks of CNTs with controlled orientation will be essential for building large-scale function devices integrated with microelectronics circuits. Bingqing Wei et al. “Lift-up growth of aligned carbon nanotube patterns” Applied Physics Letters Volume 77, Number 19 6 November 2000 and JacquelinMerikhi et al. “Sandwich growth of carbon nanotubes” Diamond & Related materials 15 (2006) pp. 104-106. - The present invention provides a low-power system and method for growing nanotubes out of carbon and other materials using a CVD, ion implantation or hybrid process with direct resistive heating of the nanotubes.
- This is accomplished by providing a growth-initiated array of nanotubes in which the nanotubes and their respective catalysts are supported on a substrate. An electrical source is connected between the substrate and a plate over the nanotubes to cause electrical current to flow through and resistively heat the nanotubes and their catalysts. The process of nanotube growth continues using a CVD or ion implantation process through completion. The direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used thereby improving heating efficiency and reducing overall power consumption. A sensed condition indicative of the temperature of the nanotubes is suitably fed back to control the electrical source to maintain a temperature within a desired range for optimal growth.
- In an embodiment, opposite ends of the nanotubes are physically bonded to the substrate and the plate. The electrical source is a current source that supplies the electrical current to the nanotubes. The plate may be lifted by the growth of nanotubes. Alternately, a mechanical actuator can lift the plate. The actuator can be controlled to either match the growth rate or to exert a small pulling force on the nanotubes to increase the growth rate. If the nanotubes exhibit the same chirality they should grow at the same rate. Statistically some nanotubes will grow slower than others. Those nanotubes will exhibit a lower resistance and thus draw a higher proportion of the sourced current. This additional heating should further stimulate growth to keep the growth rate of the entire array fairly uniform. If the nanotubes exhibit different chiralities they will grow at different rates. The bonds of the slower growing nanotubes will likely break thereby producing an array of only nanotubes having one chirality with the fastest growth rate.
- In another embodiment, a mechanical actuator maintains the plate at a small distance above the nanotubes. The electrical source is a voltage source, whereby application of a voltage across the gap between the free end of the nanotubes and the plate causes field emission to occur and electrical current to flow through the nanotubes. If the nanotubes exhibit the same chirality they should grow at the same rate. If the nanotubes exhibit different chiralities some of them will grow slower than the others. The actuator maintains the distance to the tallest fastest growing nanotubes. This increases the gap to the shorter nanotubes which reduces the amount of current to those nanotubes further slowing their growth. This approach can be used to filter the nanotubes by chirality, particularly the fastest growing nanotubes. To select a subset of nanotubes having a slower growth rate, the actuator may contact the plate to the tallest nanotubes in an oxygen environment to burn up the nanotubes. The actuator then maintains the plate at a distance above another subset of nanotubes having a chirality that exhibits the highest growth rate among the remaining nanotubes.
- In another embodiment, a conventional hot CVD process is used to form the growth-initiated array of nanotubes. Once direct resistive heating of the nanotubes is initiated the CVD process is run cold to improve energy efficiency. The CVD process can be configured with a single feedstock/growth chamber as per convention or the substrate can be used to separate the chamber into a feedstock chamber on one side and a growth chamber on the other. The latter approach separates nanotube growth from the noxious feedstock gases which tend to deteriorate the catalyst with byproducts over time.
- In another embodiment, an ion implantation process is used to form the growth-initiated array of nanotubes. The requisite heating can be provided indirectly by wall or substrate heating or by the energy in the ion beam itself. Once direct resistive heating of the nanotubes is initiated the indirect heat source can be removed or reduced (reduced beam energy) to improve energy efficiency. The ion implantation process can be configured with a single implantation/growth chamber or the substrate can be configured to provide an implantation region on one side and a growth region on the other. The two chambers may be held in the same vacuum or the substrate may provide an environmental seal for independent control. This approach separates nanotube growth from the ion beam.
- In another embodiment, a hybrid CVD and ion implantation process is used. The substrate forms a seal creating two separate chambers. A feedstock/growth chamber is formed on one side of the substrate and an implantation chamber on the other side of the substrate. A CVD process initiates growth of the nanotube array. Current is passed through the nanotubes to provide the direct resistive heating. At this point, either the CVD process can be run cold for awhile before switching to the ion implantation process or the ion implantation process can start immediately. The hybrid approach combines the fast growth capability of the CVD process to initiate growth with the sustained growth capability of ion implantation to grow nanotubes of arbitrary length.
- These and other features and advantages of the invention will be apparent to those skilled in the art from the following detailed description of preferred embodiments, taken together with the accompanying drawings, in which:
-
FIG. 1 , as described above, is a diagram of a carbon nanotube; -
FIGS. 2 a-2 b, as described above, are diagrams illustrating root and tip CNT growth; -
FIG. 3 , as described above, is a diagram of a conventional CVD process using a single feedstock-growth chamber to grow CNTs on a substrate; -
FIGS. 4 a and 4 b, as described above, are diagrams of a CVD “lift-off” process for growing an array of CNTs that lifts a metal thin-film; -
FIGS. 5 a and 5 b are physical and electrical schematic diagrams of a current source connected across a growth-initiated CNT array to provide direct resistive heating of the nanotubes and their respective catalysts; -
FIGS. 6 a through 6 c are diagrams of carbon nanotubes illustrating armchair, zig-zag and chiral orientations, respectively; -
FIGS. 7 a and 7 b are diagrams of a voltage source connected between a growth-initiated CNT array and a plate to stimulate field emission to provide direct resistive heating of the nanotubes and their catalysts for single and multiple chirality growth, respectively; -
FIG. 8 is a diagram of a feedstock/growth chamber for a low-power CVD process; -
FIG. 9 is a diagram of a low-power CVD process in which the substrate separates the feedstock and growth chambers; -
FIG. 10 is a diagram of an implantation/growth chamber for a low-power ion implantation process; -
FIG. 11 is a diagram of a low-power ion implantation process in which the substrate separates implantation and growth regions; -
FIG. 12 is a diagram of a low-power hybrid CVD-ion implantation process in which the substrates isolates an implantation chamber from a feedstock/growth chamber; and -
FIG. 13 is a diagram of a single nanotube in which a second catalyst has been formed within the nanotube. - The present invention provides a low-power system and method for growing nanotubes out of carbon and other materials such as Germanium, Boron, Boron-Nitride, Boron-Carbide, BiCjNk where i, j and k are any non-negative integers, Silicon and Silicon-Carbide using a CVD, ion implantation or hybrid process with direct resistive heating of the nanotubes. This is accomplished by providing a growth-initiated array of nanotubes. An electrical source is connected between the substrate and a plate over the nanotubes (in contact with or separated by a small gap) to cause electrical current to flow through the nanotubes producing direct resistive heating of the nanotubes and their catalysts. The process of nanotube growth continues using a CVD or ion implantation process through completion. The direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used thereby improving heating efficiency and reducing overall power consumption. A sensed condition indicative of the temperature of the nanotubes is suitably fed back to control the electrical source to maintain a temperature within a desired range for optimal growth.
- As shown in
FIGS. 5 a and 5 b, some process such as CVD or ion implantation is used to provide a growth-initiated array ofnanotubes 60 in which the nanotubes and theirrespective catalysts 62 are supported between and bonded to asubstrate 64 and aplate 66.Plate 66 is suitably a metal thin-film such as nickel provided via a lift-off process. In this embodiment, the nanotubes are grown via lip growth'. The nanotubes may be alternately grown via ‘root growth’ or both. Either growth process uses some type of indirect heating to heat the catalysts to initiate nanotube growth. Indirect heating is an inefficient approach to heating the catalysts because much energy is expended to heat the environment inside the chamber, substrate, chamber walls etc. However, it is needed to initiate nanotube growth. - To reduce the go-forward, hence total power consumption, a
current source 68 is connected across thesubstrate 64 and thin-film 66, which are configured to provide electrical contacts at opposite ends of the nanotubes, to close an electrical circuit. The substrate and thin-film typically conduct electrical current. Alternately, conductive traces or paths could be formed in either or both if non-conductive. The current source sources electricalcurrent i S 70 that flows through the nanotubes as iNT 72 producing directresistive heating 74 of the nanotubes and their catalysts (and the nearby surrounding gas in a CVD process). Acontroller 76 suitably controls the amount ofcurrent i S 70 to maintain the nanotube temperature in a desired range for optimal growth. Typical ranges for carbon nanotube growth are 400 to 1000 degrees Celsius. Closer tolerances in temperature may be required in certain process controls. The initial current is set based on a calculation or empirical evidence of the estimated number of nanotubes and average resistance. The control may operate open-loop depending on the temperature tolerances. Alternately, one ormore sensors 78 suitably sense a condition indicative of the temperature of the nanotubes that is fed back to thecontroller 76 to control the current source to maintain the temperature within the desired range. The sensed condition may be the temperature of the nanotubes or another parameter correlated to temperature. In one embodiment, an optical pyrometer outside the chamber is used to directly sense the temperature inside the chamber. An optical pyrometer generally senses the maximum temperature in an imaged area. The thin-film may be lifted by the growth of nanotubes. Alternately, amechanical actuator 80 such as a piezo actuator can lift the thin-film 66. The actuator can be controlled to either match the growth rate or to exert a small pulling force on the nanotubes to place them under tensile stress and increase the growth rate. The process of nanotube growth continues using a growth process such as CVD or ion implantation through completion. The direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used thereby improving heating efficiency and reducing overall power consumption. - As mentioned above, the
carbon nanotubes 60 grow as a hollow cylindrical shaped carbon molecule built from a hexagonal lattice of sp2 bonded carbon atoms with no dangling bonds. As shown inFIGS. 6 a through 6 c, the orientation of the hexagonal lattice can exhibit different ‘chirality’e.g. armchair 82, zig-zag 84, and chiral 86. The different chiralities exhibit different electrical and thermal conductivities and different growth rates. Typically, the array of carbon nanotubes will exhibit different chiralities somewhat randomly across the array. The bonds of the slower growing nanotubes will likely break (the CNT being much stronger than the bond between the CNT and substrate or thin-film) thereby producing an array of only nanotubes having one chirality with the fastest growth rate. If the growth process can be controlled so that all nanotubes exhibit the same chirality they should grow at the same rate. Statistically some nanotubes will grow slower than others even if they are the same chirality. Those nanotubes will exhibit a lower resistance RNT and thus draw a higher proportion of the sourced current. This additional heating should further stimulate growth to keep the growth rate of the entire array fairly uniform for one chirality. A system and method for growing carbon nanotube arrays of one chirality is disclosed in co-pending U.S. application Ser. No. ______ entitled “System and Method of Cloning an Epitaxially Generated Precursor Chiral Nanotube” filed on ______, 2008, the contents of which are incorporated by reference. - As shown in
FIG. 7 a, a process such as CVD or ion implantation is used to provide a growth-initiated array ofnanotubes 90 in which thenanotubes 90 and theirrespective catalysts 92 are supported on asubstrate 94. In this embodiment, the nanotubes are grown via ‘root growth’. The nanotubes may be alternately grown via ‘tip growth’ or both. Either growth process uses some type of indirect heating to heat the catalysts to initiate nanotube growth. Indirect heating is an inefficient approach to heating the catalysts because much energy is expended to heat the environment inside the chamber, substrate, chamber walls etc. However, it is needed to initiate nanotube growth. - Once nanotube growth is initiated, the array is heated using direct resistive heating. A
mechanical actuator 96 maintains aplate 98 at a small distance above the nanotubes. Avoltage source 100 connected across thesubstrate 94 andplate 98 applies a voltage across agap 102 between thefree end 104 of thenanotubes 90 and theplate 98 causing field emission ofelectrons 106 to occur and electricalcurrent i NT 108 to flow through thenanotubes 90 producing directresistive heating 110 of the nanotubes and their catalysts (and the surrounding gas in a CVD process). Acontroller 112 controls the voltage level and/or theactuator 96 controls the gap to adjust the current level to maintain the nanotube temperature in a desired range for optimal growth. The initial voltage is set based on a calculation or empirical evidence of the estimated number of nanotubes and average resistance. The controller may simply fix the voltage level or vary it based on calculations or empirical evidence. Alternately, one ormore sensors 114 suitably sense a condition indicative of the temperature of the nanotubes, which is fed back to thecontroller 112 to control the voltage source and/or mechanical actuator to maintain the temperature within the desired range. The sensed condition may be the temperature of the nanotubes or another parameter correlated to temperature. The process of nanotube growth continues using a CVD or ion implantation process through completion. The direct resistive heating of the nanotubes replaces or reduces the indirect heating typically used to improve heating efficiency and reduce overall power consumption. - As mentioned above, the carbon nanotubes may exhibit different chiralities. If, as depicted in
FIG. 7 a, thenanotubes 90 exhibit the same chirality they should grow at the same rate. If, as depicted inFIG. 7 b, thenanotubes 90 exhibit different chiralities some of them will grow slower than the others. Theactuator 96 maintains the distance to the tallest fastest growing nanotubes. This increases the gap to the shorter nanotubes which reduces the amount of current to those nanotubes further slowing their growth. If the gap is large enough field emission, hence current flow will cease. This approach can be used to filter the nanotubes by chirality, particularly the fastest growing nanotubes. To select a subset of nanotubes having a slower growth rate,oxygen gas 116 is fed into the chamber vialine 118 and the actuator contacts the plate to the tallest nanotubes to burn up the nanotubes. The oxygen is pumped out of the chamber and actuator then maintains the plate at a distance above another subset of nanotubes having a chirality that exhibits the highest growth rate among the remaining nanotubes. - Direct resistive heating to grow nanotubes out of carbon and other materials can be implemented with, for example, CVD, ion implantation or hybrid growth processes. Both the current and voltage source embodiments can be used with any of these or other growth processes. By way of example only, each of these growth processes will be described in context of the current source embodiment.
- A conventional hot CVD process can be used to form the growth-initiated array of nanotubes. Once direct resistive heating of the nanotubes is initiated the CVD process is run cold to improve energy efficiency. The CVD process can be configured with a single feedstock/growth chamber as per convention (
FIG. 8 ) or the substrate can be configured with catalyst material embedded therein that provides a feedstock chamber on one side and a growth chamber on the other (FIG. 9 ). The latter approach separates nanotube growth from the noxious feedstock gases. The latter approach is detailed in co-pending U.S. application Ser. No. 11/969,533 entitled “Carbon Nanotube Growth via Chemical Vapor Deposition using a Catalytic Transmembrane to Separate Feedstock and Growth Chambers” filed on Jan. 4, 2008, the contents of which are incorporated by reference. - As shown in
FIG. 8 , to synthesizeCNTs 124 using CVD thesubstrate 122 andcatalyst 120 with a thin-film 126 thereon are placed inside an environmentally controlledchamber 132. A plurality of gas feeds 134 introduce a process gas including a mixture of a carbon-containinggrowth gas 136, typically a hydrocarbon CxHy such as Ethylene (C2H4), Methane (CH4), Ethanol (C2H5OH), or Acetylene (C2H2) or possibly a non-hydrocarbon such as carbon-monoxide (CO), aninert buffer gas 138 such Argon (Ar) to control pressure inside the chamber and prevent released hydrogen atoms from exploding and possibly ascrubber gas 140 such as H2O or O2 to periodically or continuously clean the surface of the catalyst. Anenergy source 142 such as induction, plasma discharge, substrate or wall heating provides the energy necessary (e.g. a few eV) for a hot CVD process to heat the catalyst to a temperature which allows it to ‘crack’ the hydrocarbon molecules into reactiveatomic carbon 144, to heat the catalyst to increase the transport of carbon to the catalysts/CNT interface and to heat the CNT itself. Thereactive carbon 144 is absorbed into the surface ofcatalyst 120 causing theCNT 124 to grow from the same catalytic surface and lift-thin film 126. Apump system 146 including a vacuum and/or pressure pump controls the pressure inside the chamber to produce conditions both conducive to absorption of carbon atoms into the catalytic material and growth of CNTs from the catalytic material. A number ofports 148 are provided to accommodate pressure sensors, thermocouples and the like to monitor conditions inside the chamber. - A direct resistive heating system includes a
current source 150 that is electrically connected throughports 148 betweensubstrate 122 and thin-film 126 to source current through the parallel-combination ofnanotubes 124, atemperature sensor 152 such as an optical pyrometer that that senses the temperature of the nanotubes through aport 148 and acontroller 154 that processes the temperature data to adjust the total source current to maintain the temperature in a desired range for optimal nanotube growth. Once growth is initiated,energy source 142 is suitably turned off and the heat required to crack the hydrocarbon molecules colliding with the catalyst, heat the catalyst for more rapid diffussion and to heat the CNT is provided by the directresistive heating 156. The energy and power required to operate the current source is far less than the energy required to operateindirect energy source 142. - As shown in
FIG. 9 , direct resistive heating can also be used in conjunction with a modified CVD process in which thesubstrate 122 is secured by agasket 160 to separate the chamber into afeedstock chamber 162 and agrowth chamber 164 in which the growth-gas is confined to the feedstock chamber. Thecatalysts 120 are embedded in the substrate withportions 166 of catalyst surface exposed to the feedstock chamber for absorbingcarbon atoms 144 from the growth gas and different portions ofcatalyst surface 168 exposed to the growth chamber to grownanotubes 124 in an environment devoid of said growth gas. A vacuum or pressure pump 170 controls the pressure in the growth chamber. Abuffer gas 172 may be fed into the chamber throughlines 174 if desired.Substrate 122 is suitably quite thin, a few millimeters thick. Consequently the direct heating of the CNTs and catalysts in the growth chamber efficiently heats the gases in the feed stock chamber providing sufficient energy to ‘crack’ the hydrocarbon molecules which come into contact with the hot tubes and catalysts. - An ion implantation process can be used to form the growth-initiated array of nanotubes. Once direct resistive heating of the nanotubes is initiated the indirect heat source used to initiate growth is turned off or at least reduced to improve overall energy efficiency. The ion implantation process can be configured with a single implantation/growth chamber (
FIG. 10 ) or the substrate can be configured with catalyst material embedded therein or thereon that provides an implantation region on one side and a growth region on the other (FIG. 11 ). The latter approach separates nanotube growth from the ion beam. The ion implantation approach is detailed in co-pending U.S. application Ser. No. 12/061,317 entitled “System and Method for Nanotube Growth via Ion Implantation using a Catalytic Transmembrane” filed on Apr. 2, 2008 the contents of which are incorporated by reference. Growth rates via direct implantation are expected to be considerably slower than CVD but sustainable and may be increased by indirect implantation via “knock on” or “sputtering” processes that amplify the number of carbon ions transferred into the catalyst. Ion implantation is a more precise and controllable process than CVD that facilitates closer spacing of CNTs in an array and control of CNT length. - As shown in
FIG. 10 , asubstrate 200 having one ormore catalysts 202 supported thereon and covered by a thin-film 204 is placed inside an environmentally controlledchamber 206 held at vacuum by avacuum pump 207. Asource 208 directs a beam ofcarbon ions 210 through the thin-film to implant the ions into thecatalysts 202. The energy of the ion beam itself or anindirect energy source 212 provides the thermal energy necessary to heat the catalysts for proper diffussion and attachment of carbon atoms to initiate growth ofCNTs 214. - A direct resistive heating system includes a
current source 220 that is electrically connected throughports 222 betweensubstrate 200 and thin-film 204 to source current through the parallel-combination ofnanotubes 214, atemperature sensor 224 such as an optical pyrometer that that senses the temperature of the nanotubes through aport 222 and acontroller 226 that processes the temperature data to adjust the total source current to maintain the temperature in a desired range for optimal nanotube growth. Once growth is initiated,energy source 212 is suitably turned off or reduced (e.g. if ion beam provides heating, reduce beam energy) and the heat required to heat the catalyst for more rapid diffussion and to heat the CNT is provided by the directresistive heating 228. The energy and power required to operate thecurrent source 220 is far less than the energy required to operateindirect energy source 212 and/or to operate the ion beam at higher energy levels. - As shown in
FIG. 11 , direct resistive heating can also be used in conjunction with a modified ion implant process in whichsubstrate 200 physically separateschamber 206 into animplantation region 230 and agrowth region 232.Catalysts 202 supported on the underside of substrate 200 (or embedded in the substrate) provide animplantation surface 234 to receive carbon ions frombeam 210 with sufficient energy to reach, penetrate and stop in the catalyst and agrowth surface 236 directly exposed to the growth region to growcarbon nanotubes 214. This configuration protects the CNTs from the ion beam. In addition, “knock-on” processes can be used to increase the flux of carbon ions implanted into the catalysts. Aspacer layer 240 separates a knock on layer 242 (e.g. Graphite) from the catalyst material. An anti-sputtering layer 244 (e.g. Ti, Mo, etc.) is deposited over the knock-on layer.Source 208 directsion beam 210 through the anti-sputtering layer onto knock-onlayer 242. Through a “knock-on” process, each ion knocks multiple carbon ions forward through the substrate intocatalyst 202 thereby providing gain. In this configuration, the source does not have to emit carbon ions, it could, for example, emit heavier ions to improve knock-on efficiency. In an alternate embodiment, a gasket is fitted aroundsubstrate 200 to isolate an implantation chamber from a growth chamber. Consequently, the pressure and gas environment of the growth chamber can be independently controlled as desired. - Direct resistive heating can be similarly used in a hybrid CVD/ion implantation process. The substrate forms a seal creating two separate chambers. A feedstock/growth chamber is formed on one side of the substrate and an implantation chamber on the other side of the substrate. A CVD process initiates growth of the nanotube array. Current is passed through the nanotubes to provide the direct resistive heating. At this point, either the CVD process can be run cold for awhile before switching to the ion implantation process or the ion implantation process can start immediately. The hybrid approach combines the fast growth capability of the CVD process to initiate growth with the sustained growth capability of ion implantation to grow nanotubes of arbitrary length.
- As shown in
FIG. 12 , to initiate nanotube growth using CVD asubstrate 300 with one ormore catalysts 302 on the underside of the substrate or embedded therein and with a thin-film 304 over the catalysts is placed inside an environmentally controlledchamber 306. Agasket 308 holds thesubstrate 300 to form a seal that separates the chamber into a feedstock andgrowth chamber 310 for CVD and animplantation chamber 312 for ion implantation. - A plurality of gas feeds 314 introduce a process gas including a mixture of a carbon-containing
growth gas 316, typically a hydrocarbon CxHy such as Ethylene (C2H4), Methane (CH4), Ethanol (C2H5OH), or Acetylene (C2H2) or possibly a non-hydrocarbon such as carbon-monoxide (CO), aninert buffer gas 318 such Argon (Ar) to control pressure inside the chamber and prevent released hydrogen atoms from exploding and possibly ascrubber gas 320 such as H2O or O2 to periodically or continuously clean the surface of the catalyst. Anenergy source 322 such as induction, plasma discharge, substrate or wall heating provides the energy necessary (e.g. a few eV) for a hot CVD process to heat the catalyst to a temperature which allows it to ‘crack’ the hydrocarbon molecules into reactiveatomic carbon 323, to heat the catalyst to increase the transport of carbon to the catalysts/CNT interface and to heat the CNT itself. The reactive carbon is absorbed into the exposed surface ofcatalyst 302 to initiate growth ofCNT 324 to grow from the same catalytic surface and lift-thin film 304. Apump system 326 including a vacuum and/or pressure pump controls the pressure inside the chamber to produce conditions both conducive to absorption of carbon atoms into the catalyst and growth of CNTs from the catalyst. - A direct resistive heating system includes a
current source 330 that is electrically connected throughports 332 betweensubstrate 300 and thin-film 304 to source current through the parallel-combination ofnanotubes 324, atemperature sensor 334 such as an optical pyrometer that that senses the temperature of the nanotubes through aport 332 and acontroller 336 that processes the temperature data to adjust the total source current to maintain the temperature in a desired range for optimal nanotube growth. Once growth is initiated,energy source 332 is suitably turned off and the heat required to heat the catalyst for more rapid diffussion and to heat the CNT is provided by the directresistive heating 338. - At this point, either the CVD process can be run cold for awhile before switching to the ion implantation process or the ion implantation process can start immediately. A
vacuum pump 340 holds theimplantation chamber 312 at vacuum. Asource 342 directs a beam ofions 344 towards the substrate to causecarbon ions 346 to be implanted intocatalyst 302. The beam may inject carbon ions directly into the catalysts or amplify them, as shown, using ‘knock-on’ processes. Aspacer layer 348 separates a knock on layer 350 (e.g. Graphite) from the catalyst material. An anti-sputtering layer 352 (e.g. Ti, Mo, etc.) is deposited over the knock-on layer.Source 342 directsion beam 244 through the anti-sputtering layer onto knock-onlayer 350. Through a “knock-on” process, each ion knocks multiple carbon ions forward through the substrate intocatalyst 302 thereby providing gain. - Direct resistive heating is used to effectively and energy efficiently grow one or more nanotubes. In addition to proper and efficient heating, nanotube growth can be further stimulated by the formation of additional catalysts within the nanotubes as they grow. As shown in
FIG. 13 , root growth of acatalyst 400 onsubstrate 402 produces ananotube 404. An element-containing gas ormist 406, for example, is introduced into the chamber environment through agas feed 408. Anelectron beam 410 bombards the nanotubes in the element-containing environment to form anadditional catalyst 412 at the tip of the growing nanotubes. In this embodiment, the tip is attached to a thin-film 414 to support the direct resistive heating. In the field emission embodiment, the tip may be unattached. Theadditional catalyst 412 may grow the nanotube via root or tip growth. The process can be repeated for anothercatalyst 414 on the free end of the nanotube. - This process for forming additional catalysts within the nanotubes to further stimulate and speed growth is not limited to direct resistive heating, the process can be used in any of the CVD or ion implantation processes with or without direct resistive heating.
- Although the description of the invention has focused on the growth of carbon nanotubes the approach is viable for growing nanotubes from other materials such as Germanium (Ge), Boron (B), Boron-Nitride (BN), Boron-Carbide, BiCjNk, Silicon (Si) or Silicon-Carbide (SiC). The interest in and development of carbon nanotube technology is well beyond that of other materials, hence the focus on carbon nanotubes. However, the approach of using direct resistive heating to grow nanotubes from these other or yet to be discovered materials is equally applicable.
- While several illustrative embodiments of the invention have been shown and described, numerous variations and alternate embodiments will occur to those skilled in the art. Such variations and alternate embodiments are contemplated, and can be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (30)
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US20120318455A1 (en) * | 2011-06-14 | 2012-12-20 | Andreas Fischer | Passive compensation for temperature-dependent wafer gap changes in plasma processing systems |
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CN102380133B (en) * | 2011-10-20 | 2013-09-11 | 天津师范大学 | Multi-walled carbon nanotube injected with carboxyl ions, preparation method and application thereof |
JP5909826B2 (en) * | 2012-05-11 | 2016-04-27 | 住友電気工業株式会社 | Method for producing carbon nanostructure |
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