The present invention relates to the engineering of bends in high-aspect-ratio nanostructures, in particular, catalytically grown carbon nanotubes containing multiple sharp bends.
Since their discovery carbon nanotubes (CNTs) have been studied for many different applications because of their exceptional electrical and mechanical properties. Carbon nanotubes have already been shown to be useful for a variety of applications, such as field emission devices, nano-scale electromechanical actuators, field-effect transistors (FETs), CNT based random access memory (RAM), and atomic force microscope (AFM) probes. There has also been much work demonstrating CNTs potential as nano-interconnects, including showing no obvious degradation after 350 hours in the current carrying capacities of multiwalled CNTs (MWNTs) at very high current densities of 1010 A/cm2, the manufacture of deterministic CNT wiring networks, and using an electron beam to form mechanical connections between two nanotubes.
In order to utilize CNTs as interconnects and other device components, the ability to control their growth morphology is desired. The growth of vertically aligned MWNTs has been demonstrated by several groups using plasma enhanced chemical vapor deposition (PECVD). See articles by Ren, et al., “Synthesis of large arrays of well-aligned carbon nanotubes on glass”, Science 282, page 1105 (1998), by Bower, et al., “Plasma-induced alignment of carbon nanotubes”, Appl. Phys. Lett., 77, 830-832 (2000), and “Nucleation and growth of carbon nanotubes by microwave plasma chemical vapor deposition”, Appl. Phys. Lett., 77, 2767-2769 (2000), and by Merkulov, et al., “Alignment Mechanism of Carbon Nanofibers Produced by Plasma-Enhanced Chemical-Vapor Deposition”. Appl. Phys. Lett. 79, 2970-2972 (2001).
These results all had CNTs aligned perpendicular to a substrate surface due to the applied field or electrical self-bias field created by-the plasma environment. The linear aligned growth of CNTs by electric field in other directions, such as in-plane directions, has been demonstrated both for single walled carbon nanotubes (SWNTs) and MWNTs.
Although alignment of individual CNTs and CNT arrays has been demonstrated, there has been very little work done towards more complicated morphologies. Merkulov et. al. showed a fabrication of bent CNTs consisting of one section perpendicular to a substrate and a second section aligned ˜45° off of the substrate normal with radii of curvature on the order of 1 μm. The off-normal growth was achieved by positioning the sample near the edge of the sample holder where bending of the electric field lines occurs. This invention shows the ability to grow CNTs with sharp bends that maintain a constant tube diameter before and after a bend and the ability to grow structures with multiple bends resulting in a zigzag morphology. Zigzag structured or signally bent CNTs could be used for many applications, e.g., related to mechanical nanosprings, atomic force microscope (AFM) probes, or complicated circuit nano-interconnections.
This invention includes novel elongated nanostructures attached on a substrate, with one or more bends, methods for engineering such bent nanostructures with sharp radii of curvature of preferably less than 100 nm, and devices comprising such nanostructures for applications such as nano interconnections, nano circuit components, nano heterojunction semiconductors, nano solenoids, nano springs and various nano-manipulators/nano-actuators, nano probes for characterization of surface topography, nano conductance, nanomagnetics, nano-writing/nano-patterning, and nano machining. This invention allows for the synthesis of structures with multiple sharp bends i.e. zigzag morphology, box helixes, nano solenoids and others.
The advantages, nature, and additional features of the invention will appear more fully upon consideration of the illustrative embodiments described in the accompanying drawings. It is to be understood that these drawings are for purposes of illustrating the concepts of the invention and are not to scale. In the drawings:
This invention and the various features and advantageous details thereof are explained more fully with reference to the exemplary embodiments that are illustrated in the accompanying drawings and detailed in the following description. Descriptions of well known starting materials, processing techniques, components, and equipment are omitted so as not to obscure the invention in detail. It should be understood however, that the detailed description and the specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only and not by way of limitation. Various substitutions, modifications, additions, and/or rearrangements within the spirit and/or scope of the underlying inventive concept will become apparent to those skilled in the art from this disclosure.
This invention includes one or more elongated nanostructures having at least one sharp bend that has a radius of curvature less than 100 nm. The nanostructured material can be carbon nanotubes or other electrically conducting nanowires such as metallic nanowires, doped Si, GaN, etc., and can have either a solid or tube shape nanowires. The diameter of the inventive nanostructure is in the range of 1-500 mn, preferentially 1-100 nm. This invention includes a sharply bent nanostructure with a radius of curvature of bend of, preferably less than 100 nm radius of curvature.
This invention also includes methods of making nanostructures with sharp bends described above, either by a repeated movement of field-concentrating metal blocks or by a continuous and controlled rotation/movement of the metal blocks during deposition of nanostructures. The invention can also include apparatus for making nanostructures with sharp bends described above. The invention also includes devices comprising such bent nanostructures.
In the absence of an applied DC bias, CNT growth in a microwave plasma environment has been shown to produce CNTs aligned perpendicular to the substrate. The plasma environment creates a potential self-bias where the field lines are always perpendicular to the surface. Even when a substrate's surface is tilted at any angle, the field lines will bend and, within a narrow region (less than 10 μm above substrate surface where CNT growth occurs), the field lines will always be straight and perpendicular to the surface.
With this invention, a recessed corner cathode geometry caused very large and dramatic changes in the direction of the electric field lines in the CNT growth region. The resulting electric field lines are bent dramatically, and even for distances 10 nm above the surface, the resulting nanostructures are grown aligned at angles greatly tilted from perpendicular to the surface. By changing the cathode geometry, multiple growth segments are made connected by sharp bends with radii of curvature under 100 nm.
This changing of cathode geometry can be accomplished by moving a metal block in electrical contact with the cathode relative to a substrate. Such movement could be accomplished, as shown in
Arrays of carbon nanotubes (CNTs) with zig-zag morphology were grown using a DC plasma enhanced chemical vapor deposition (PECVD) process using Ni catalyst particles with a tip-growth mechanism, and a mixed gas of ammonia (NH3) and acetylene (C2H2). The arrays had a density of ˜2×109CNTs/cm2. They were fabricated by first sputter depositing a 50 A° M film over the surface of an n-type Si (100) substrate. The substrates were then transferred (in air) to a CVD chamber. Upon heating to ˜780° C., the Ni film breaks up into islands with average diameters of 30-40 nm. A DC bias of 550V was applied between an anode above the sample and a cathode just below the sample. Under the applied voltage, plasma formed and acetylene (C2H2) was added to the chamber flowing at 30 sccm with the total NH3 & C2H2 pressure held at 3 torr.
Electric-field-concentrating metal plates (Molybdenum slabs) 1 mm thick (the same stock as the cathode stage) were placed in electrical contact with the cathode in the vicinity of the Si substrate in two different geometries (
In the absence of an applied DC bias, CNT growth in a microwave plasma environment has been shown to produce CNTs aligned perpendicular to the substrate. The plasma environment creates a potential self-bias where the field lines are always perpendicular to the surface. Even when a substrate's surface is tilted at any angle, the field lines will bend, and within a narrow region (less than 10 μm above substrate surface where CNT growth occurs) the field lines will be always be straight and perpendicular to the surface. It has been estimated, for a microwave plasma environment with no applied DC field, that the self bias potential is on the order of 10V and the electric field has a magnitude on the order of 0.1 V/μm in the vicinity of the surface.
The application of a standard DC potential bias results in a different electric field around the sample. In this invention, the sample substrate is located on the cathode, which results in the direction of the applied bias being towards the sample. The field lines will always be perpendicular to the local surface and will bend as they move away from the surface to connect the two poles of the applied field. Within the region close to the sample surface where CNT growth occurs, the field lines will be straight and perpendicular to the surface, which results in vertically aligned CNTs, such as those shown in
In order to cause bending in the CNTs, it is necessary to manipulate the electric field such that the field lines in the growth region of the CNTs are bent. Growth along field lines at angles not perpendicular to the substrate surface has been achieved by positioning the sample near the sharp cornered edge of the sample stage where the field lines are bent towards that sharp corner direction even at distances within the growth region. However, the use of such a protruding corner field direction does not easily allow fabrication of sharply bent nanotubes.
In this invention, a different geometry was used that allowed for the presence of electric-field-concentrating metal plates to cause very large and dramatic changes in the direction of the electric field lines in the CNT growth region. The metal plates were made of the same material as the cathode stage, and were given the same potential. The resulting electric field lines in the recessed corner were bent dramatically and even for distances ˜10 nm above the surface, the resulting CNTs were grown aligned at angles greatly tilted from a perpendicular direction (to the surface). By moving the metal plates, it was possible to again dramatically alter the direction of the electric field lines, which is how sharp bends were obtained.
An SEM image of three-step zig-zag CNTs obtained by using the conductor plate arrangement of
The bends present between two growth stages have small radii of curvature of only ˜25 nm. These nanoscale bend angles, obtained using a recessed corner of metal blocks in contact, are much sharper than micrometer scale bends previously demonstrated an open (convex) corner of a metal plate. While the nanotubes have a variation of diameter determined by the initial size of the catalyst particle formed upon heating, each individual tube shows essentially the same diameter for all growth stages.
The zig-zag nanotubes of this invention can be grown through a tip-growth process or a bottom growth process. The bends are in-plane bends (in a three dimensional sense, moving away from the substrate, not on the substrate plane). This was done to simplify the set-up geometry and to make it easier to see the resulting structures. Using similar set-ups, one can engineer out of plane bends and make more complicated three dimensional structures such as, nanocoils, segmental helixes, box-helixes, or horizontal-vertical 90 degree zig-zag shapes. Motorized rotational movement and stepper-motor movement of field-concentrating-metal plates with respect to the substrate (as illustrated in
Due to their small diameter, carbon nanotubes are potentially useful as a sharp probe for atomic force microscopy (AFM). The resolution of AFM imaging is determined by the sharpness, size and shape of the probe tip.
Typical commercially available AFM probe tips are made of silicon or silicon nitride (Si3N4) which is microfabricated into a pyramid configuration. Such probes have a typical tip radius of curvature in the ˜50 nm regime thus exhibiting a limited lateral resolution, and their rigid pyramid shape does not allow easy access to narrow or deep structural features.
Referring to
An alternative way of placing the bent nanotube probe on the AFM pyramid, according to the invention, is to directly grow the aligned and bent nanotube by CVD. processing, as illustrated in
The bent nanoprobe structures of
A sharply bent nanotube such as shown in
The desired sharpness of the bend for the probe type application of the sharply bent nanotube according to the invention is typically in the range of 2-500 nm radius of curvature at the bend, preferably less than 100-200 nm, even more preferentially less than 50 nm radius of curvature. The desired diameter of the bent nanotubes is in the range of 1-500 mn, preferably 1-100 nm. The bent nanotube can be an equal-diameter nanotube or alternatively, it can be a tapered diameter nanotube with the diameter gradually decreasing toward the nanotube tip end. The desired length of the bent nanotubes is in the range of 0.1-100 micrometer, preferably in the range of 0.2-10 micrometer.
Bent CNTs can also be useful for circuit nano-interconnections as illustrated schematically in
In summary, this invention describes the structure and fabrication techniques for growth of high-aspect-ratio nanostructures, such as carbon nanotubes with one or multiple bends. The bending of the CNTs during growth was accomplished by changing the direction of the electric field lines in the growth region of the sample, utilizing recessed corner fields of conducting metal blocks. The resulting structures have abrupt, nanoscale sharp bends, and maintain substantially the same tube diameter throughout growth. Catalyst particles are still present at the tops of the zig-zag structures, so that many additional bent segments or other unique three-dimensional structures can be created. Such multiple bent nanotubes can be useful for a variety of applications including mechanical nano-spring devices, high-resolution AFM tips, and nano-circuit interconnections.
For efficient electric field alignment of growing nanowires or nanotubes, stronger electric fields are usually desirable. Such a stronger field in the edge (or protruding corner) of conducting metal elements has thus been employed to obtain a curved nanostructure. The invention described here is new and unique, in that in contrast to prior art teaching of using a stronger field, the inventive method of bending the growing nanowires utilizes directed electric fields with extremely weak electric field intensity present in the recessed corners of electrically conducting elements. The use of recessed corner fields allows for the creation of very sharply bent nanostructure.
The invention includes novel nanostructures with sharp bends, methods for engineering such bent nanostructures with sharp radii of curvature of less than 100 nm, and devices comprising such nanostructures for applications such as nano interconnections, nano circuit components, nano heterojunction semiconductors, nano solenoids, nano springs and various nano-manipulators/nano-actuators, and nano probes for characterization of surface topography, nano conductance, nanomagnetics, nano-writing/nano-patterning, and nano machining. This inventive method allows for the synthesis of structures with multiple sharp bends i.e. zigzag morphology, box helixes, and others. The inventive method also allows for the continuous fabrication of sharply bent or curved nano-structures without interupping the deposition process, and fabrication of such novel structures over large substrate large areas.
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/US05/25763 | 7/20/2005 | WO | 1/17/2007 |
Number | Date | Country | |
---|---|---|---|
60589838 | Jul 2004 | US |