Wafer scale synthesis of dense aligned arrays of single-walled carbon nanotubes

Here we present an easy one-step approach to pattern uniform catalyst lines for the growth of dense, aligned parallel arrays of single-walled carbon nanotubes (SWNTs) on quartz wafers by using photolithography or polydimethylsiloxane (PDMS) stamp microcontact printing (μCP). By directly doping an FeCl₃/methanol solution into Shipley 1827 photoresist or polyvinylpyrrolidone (PVP), various catalyst lines can be well-patterned on a wafer scale. In addition, during the chemical vapor deposition (CVD) growth of SWNTs the polymer layers play a very important role in the formation of mono-dispersed nanoparticles. This universal and efficient method for the patterning growth of SWNTs arrays on a surface is compatible with the microelectronics industry, thus enabling of the fabrication highly integrated circuits of SWNTs.     

Guided growth of large-scale, horizontally aligned arrays of single-walled carbon nanotubes and their use in thin-film transistors

A convenient process for generating large-scale, horizontally aligned arrays of pristine, single-walled carbon nanotubes (SWNTs) is described. The approach uses guided growth, by chemical vapor deposition (CVD), of SWNTs on miscut single-crystal quartz substrates. Studies of the growth reveal important relationships between the density and alignment of the tubes, the CVD conditions, and the morphology of the quartz. Electrodes and dielectrics patterned on top of these arrays yield thin-film transistors that use the SWNTs as effective thin-film semiconductors. The ability to build high-performance devices of this type suggests significant promise for large-scale aligned arrays of SWNTs in electronics, sensors, and other applications.     

单壁碳纳米管束的排布

流体排布法是实现碳纳米管定向排列的一种简单的方法。采用流体排布法在具有浸润性图案化的基底上成功地对单壁碳纳米管(SWNTs)束进行了水平方向上的排布。将SWNTs悬浮液滴入光刻胶制成的微通道中,在流体剪切力作用下,弯曲的SWNTs在一定程度上会被拉伸并且平行地排列在纳米级宽度的微通道中。将排列好的SWNTs阵列转移到一些不同间距的金电极对上面,制作成碳纳米管场效应晶体管(CNTFET)。CNTFET的电性能测试结果表明,制备的SWNTs束可以制造出不同电极间距同时具有良好电性能的CNTFET。     

Printed multilayer superstructures of aligned single-walled carbon nanotubes for electronic applications

We developed means to form multilayer superstructures of large collections of single-walled carbon nanotubes (SWNTs) configured in horizontally aligned arrays, random networks, and complex geometries of arrays and networks on a wide range of substrates. The approach involves guided growth of SWNTs on crystalline and amorphous substrates followed by sequential, multiple step transfer of the resulting collections of tubes to target substrates, such as high-k thin dielectrics on silicon wafers, transparent plates of glass, cylindrical tubes and other curved surfaces, and thin, flexible sheets of plastic. Electrical measurements on dense, bilayer superstructures, including crossbars, random networks, and aligned arrays on networks of SWNTs reveal some important characteristics of representative systems. These and other layouts of SWNTs might find applications not only in electronics but also in areas such as optoelectronics, sensors, nanomechanical systems, and microfluidics.     

Copper catalyzing growth of single-walled carbon nanotubes on substrates

Metallic copper, which is normally considered as a contaminant in the growth of single-walled carbon nanotubes (SWNTs), was found to be an efficient catalyst to grow SWNTs under suitable conditions. It showed very high catalytic activity for the growth of both random SWNT networks and horizontally aligned SWNT arrays. Especially, high-quality SWNT arrays were obtained when monodispersed copper nanoparticles were used. The catalytic behavior of copper for the growth of SWNTs was discussed. The weaker interaction between the copper and silica surfaces plays an important role in the growth of high-quality horizontally aligned SWNT arrays. This new synthesis process of SWNTs with a non-ferromagnetic catalyst brings more convenience to the study of magnetic properties of SWNTs and gives more insight in structure-controlled synthesis of SWNTs.     

Effect of constructive rehybridization on transverse conductivity of aligned single-walled carbon nanotube films

Alignment of densely packed single-walled carbon nanotubes (SWNTs) largely preserves the extraordinary electronic properties of individual SWNTs in the alignment direction, while in transverse direction the films are very resistive due to large energy barriers for tunneling between adjacent SWNTs. We demonstrate that chromium atoms inserted between the sidewalls of parallel SWNTs effectively coordinate to the benzene rings of the nanotubes via hexahapto bonds that preserve the nanotube-conjugated electronic structure and serve as a conduit for electron transfer. The atomically interconnected aligned SWNTs exhibit enhanced transverse conductivity, which increases by ～2100% as a result of the photoactivated organometallic functionalization with Cr. The hexahapto mode of bonding the graphitic surfaces of carbon nanotubes with transition metal atoms offers an attractive route to the reversible chemical engineering of the transport properties of aligned carbon nanotube thin films. We demonstrate that a device fabricated with aligned SWNTs can be reversibly switched between a state of high electrical conductivity (ON) by light and low electrical conductivity (OFF) by applied potential. This study provides a route to the design of novel nanomaterials for applications in electrical atomic switches, optoelectronic and spintronic devices.     

Wafer‐Scale Fabrication of Suspended Single‐Walled Carbon Nanotube Arrays by Silver Liquid Dynamics

Suspended single‐walled carbon nanotubes (SWNTs) have advantages in mechanical resonators and highly sensitive sensors. Large‐scale fabrication of suspended SWNTs array devices and uniformity among SWNTs devices remain a great challenge. This study demonstrates an effective, fast, and wafer‐scale technique to fabricate suspended SWNT arrays, which is based on a dynamic motion of silver liquid to suspend and align the SWNTs between the prefabricated palladium electrodes in high temperature annealing treatment. Suspended, strained, and aligned SWNTs are synthesized on a 2 × 2 cm² substrate with an average density of 10 tubes per micrometer. Under the optimal conditions, almost all SWNTs become suspended. A promising formation model of suspended SWNTs is established. The Kelvin four‐terminal resistance measurement shows that these SWNT array devices have extreme low contact resistance. Meanwhile, the suspended SWNT array field effect transistors are fabricated by selective etching of metallic SWNTs using electrical breakdown. This method of large‐scale fabrication of suspended architectures pushes the study of nanoscale materials into a new stage related to the electrical physics and industrial applications.     

Direct observation of the strong interaction between carbon nanotubes and quartz substrate

We present a chemical vapor deposition (CVD) method for the growth of uniform single-walled carbon nanotube (SWNT) arrays on a stable temperature (ST)-cut single crystal quartz substrate using a mixture of methanol and ethanol as carbon source. It is found that introducing methanol during the growth can improve the density and the length of the well-aligned SWNTs in the arrays as well as increase the SWNT/quartz interaction. Obvious “up-shifts” of G-band frequencies in the Raman spectra have been found for the aligned SWNTs. A welldesigned control experiment shows that the G-band “up-shifts” originate from the strong interaction between SWNTs and the quartz substrate. It is believed that exploring this interaction will help to elucidate the growth mechanism; ultimately, this will help realize the promise of controlling the chirality of SWNTs.     

Templating of self-alignment patterns of anisotropic gold nanoparticles on ordered SWNT macrostructures

We report a simple and versatile technique for oriented assembly of gold nanorods on aligned single-walled carbon nanotube (SWNT) macrostructures, such as thin nanotube films and nanotube fibers. The deposition and assembly is accomplished via drop drying of dilute gold nanorod suspensions on SWNT macrostructures under ambient conditions. Guided by anisotropic interactions, gold nanorods, and polygonal platelets spontaneously align with SWNTs, resulting in macroscopic arrays of locally ordered nanorods supported on aligned SWNT substrates. SEM reveals that the scalar order parameter of rods relative to the local average SWNT alignment is 0.7 for rods on SWNT films and 0.9 for rods on SWNT fibers. This self-alignment is enabled by anisotropic gold nanoparticle-SWNT interactions and is observed for a wide range of nanoparticles, including nanorods with aspect ratios ranging from 2-35, thin gold triangular and other polygonal platelets. The plasmonic properties of aligned gold nanorods together with superior electronic, chemical and mechanical properties of SWNTs make these hybrid nanocomposites valuable for the design of self-assembled multifunctional optoelectronic materials and optical metamaterials.     

Catalyst-free growth of oriented single-walled carbon nanotubes on mica by ethanol chemical vapor deposition

In this letter, it is reported for the first time that single-walled carbon nanotubes (SWNTs) can grow on mica substrate without additional catalyst by chemical vapor deposition (CVD) using ethanol as carbon source. The single-wall structure was characterized by Raman spectra and AFM (Atomic Force Microscopy) measurements. The growth of carbon nanotubes on mica surface contributes to the small amount of iron oxide in bare mica. The uniform dispersion and nanosized Fe particles formed from the reduction of iron oxide favor for the growth of SWNTs. Horizontally aligned superlong SWNTs arrays can be successfully generated on the mica surface, which is proved to be guided by the gas flow and under “kite growth mechanism”. The mica is a machinable material which can be easily cut and made a narrow slit on, thus the nanotubes can traverse the slit which can be in millimeter scale and long suspended SWNTs can be generated. This will provide an opportunity to manipulate individual SWNT for various purposes.     

High‐Performance Partially Aligned Semiconductive Single‐Walled Carbon Nanotube Transistors Achieved with a Parallel Technique

Single‐walled carbon nanotubes (SWNTs) are widely thought to be a strong contender for next‐generation printed electronic transistor materials. However, large‐scale solution‐based parallel assembly of SWNTs to obtain high‐performance transistor devices is challenging. SWNTs have anisotropic properties and, although partial alignment of the nanotubes has been theoretically predicted to achieve optimum transistor device performance, thus far no parallel solution‐based technique can achieve this. Herein a novel solution‐based technique, the immersion‐cum‐shake method, is reported to achieve partially aligned SWNT networks using semiconductive (99% enriched) SWNTs (s‐SWNTs). By immersing an aminosilane‐treated wafer into a solution of nanotubes placed on a rotary shaker, the repetitive flow of the nanotube solution over the wafer surface during the deposition process orients the nanotubes toward the fluid flow direction. By adjusting the nanotube concentration in the solution, the nanotube density of the partially aligned network can be controlled; linear densities ranging from 5 to 45 SWNTs/μm are observed. Through control of the linear SWNT density and channel length, the optimum SWNT‐based field‐effect transistor devices achieve outstanding performance metrics (with an on/off ratio of ~3.2 × 10⁴ and mobility 46.5 cm²/Vs). Atomic force microscopy shows that the partial alignment is uniform over an area of 20 × 20 mm² and confirms that the orientation of the nanotubes is mostly along the fluid flow direction, with a narrow orientation scatter characterized by a full width at half maximum (FWHM) of <15° for all but the densest film, which is 35°. This parallel process is large‐scale applicable and exploits the anisotropic properties of the SWNTs, presenting a viable path forward for industrial adoption of SWNTs in printed, flexible, and large‐area electronics.     

Chemical vapour deposition of single walled carbon nanotubes freely suspended over nanotube supports

Single walled carbon nanotubes (SWNTs) suspended above the substrate can be fabricated simply and rapidly by chemical vapour deposition growth over pre-grown multi-walled carbon nanotubes (MWNTs). SWNTs are suspended either on a randomly organized carbon nanotube network on an unpatterned substrate, or between organized pillars made from vertically aligned nanotube forests on a patterned substrate. All nanotubes are produced during a single growth run using a two step growth technique. This approach enables the fabrication of laterally suspended SWNT networks which are well suited for optical applications.     

Cadmium-catalyzed surface growth of single-walled carbon nanotubes with high efficiency

We demonstrate that cadmium (Cd) can catalyze the growth of single-walled carbon nanotubes (SWNTs) with high efficiency. The Cd nanocatalysts, prepared using a diblock copolymer templating method, were uniformly spaced over a large deposition area with an average diameter of 1.9 nm and narrow size distribution. By using the normal-heating and fast-heating method, random and horizontally aligned arrays of SWNTs can be generated. The density of the SWNTs can be altered by the chemical vapor deposition conditions. The morphology and microstructure of the SWNTs characterized by scanning electron microscopy, Raman spectroscopy, atomic force microscopy, and high-resolution transmission electron microscopy revealed that the grown nanotubes do not have carbonaceous particles and have good crystallinity. In addition, after careful check with superlong nanotubes 735 out of 790 nanotubes were found to be deposited with Ag (93%) and only 7% SWNTs without Ag deposition. While for superlong SWNT arrays from Fe, 32% long SWNTs without Ag deposition was found, the high percentage of SWNTs with Ag deposition from Cd indicates that the SWNTs have better conductivity and better structural uniformity with less defects.     

Controlled growth of single-walled carbon nanotubes for unique nanodevices

The controlled growth of bent and horizontally aligned single-walled carbon nanotubes (SWNTs) is demonstrated in this study. The bent SWNTs growth is attributed to the interaction between van der Waals force with substrate and aerodynamic force from gas flow. The curvature of bent SWNTs can be tailored by adjusting the angle between gas flow and step-edge direction. Electrical characterization shows that the one-dimensional resistivity of bent SWNTs is correlated with the curvature, which is due to strain induced energy bandgap variation. Additionally, a downshift of 10 cm(-1) in G-band is found at curved part by Raman analysis, which may be resulted from the bending induced carbon-carbon bond variation. In addition, horizontally aligned SWNTs and crossbar SWNTs were demonstrated. To prove the possibility of integrating the SWNTs having controllable morphology in carbon nanotube based electronics, an inverter with a gain of 2 was built on an individual horizontally aligned carbon nanotube.     

High-performance electronics using dense, perfectly aligned arrays of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have many exceptional electronic properties. Realizing the full potential of SWNTs in realistic electronic systems requires a scalable approach to device and circuit integration. We report the use of dense, perfectly aligned arrays of long, perfectly linear SWNTs as an effective thin-film semiconductor suitable for integration into transistors and other classes of electronic devices. The large number of SWNTs enable excellent device-level performance characteristics and good device-to-device uniformity, even with SWNTs that are electronically heterogeneous. Measurements on p- and n-channel transistors that involve as many as approximately 2,100 SWNTs reveal device-level mobilities and scaled transconductances approaching approximately 1,000 cm(2) V(-1) s(-1) and approximately 3,000 S m(-1), respectively, and with current outputs of up to approximately 1 A in devices that use interdigitated electrodes. PMOS and CMOS logic gates and mechanically flexible transistors on plastic provide examples of devices that can be formed with this approach. Collectively, these results may represent a route to large-scale integrated nanotube electronics.     

Anisotropic thermal diffusivity characterization of aligned carbon nanotube-polymer composites

The anisotropic thermal diffusivity of aligned carbon nanotube-polymer composites was determined using a photothermoelectric technique. The composites were obtained by infiltrating poly-dimethyl siloxane (PDMS) in aligned multiwall CNT arrays grown by chemical vapor deposition on silicon substrates. The thermal diffusivities are insensitive to temperature in the range of 180 K-300 K. The thermal diffusivity values across the alignment direction are approximately 2-4 times smaller than along the alignment direction and larger than effective media theory predictions using reported values for the thermal diffusivity of millimeter thick aligned multiwall carbon nanotube arrays. The effective room temperature thermal conductivity of the composite along the carbon nanotube alignment direction is at least 6X larger than the thermal conductivity of the polymer matrix and is in good agreement with the effective media predictions. This work indicates that infiltration of long and aligned carbon nanotube arrays is currently the most efficient method to obtain high thermal conductivity polymer composites.     

Experimental and theoretical studies of transport through large scale, partially aligned arrays of single-walled carbon nanotubes in thin film type transistors

Gate-modulated transport through partially aligned films of single-walled carbon nanotubes (SWNTs) in thin film type transistor structures are studied experimentally and theoretically. Measurements are reported on SWNTs grown by chemical vapor deposition with systematically varying degrees of alignment and coverage in transistors with a range of channel lengths and orientations perpendicular and parallel to the direction of alignment. A first principles stick-percolation-based transport model provides a simple, yet quantitative framework to interpret the sometimes counterintuitive transport parameters measured in these devices. The results highlight, for example, the dramatic influence of small degrees of SWNT misalignment on transistor performance and imply that coverage and alignment are correlated phenomena and therefore should be simultaneously optimized. The transport characteristics reflect heterogeneity in the underlying anisotropic metal-semiconductor stick-percolating network and cannot be reproduced by classical transport models.     

Lithography-free in situ Pd contacts to templated single-walled carbon nanotubes

We report a metalization technique for electrically addressing templated vertical single-walled carbon nanotubes (SWNTs) using in situ palladium (Pd) nanowires. SWNTs are synthesized from an embedded catalyst in a modified porous anodic alumina (PAA) template. Pd is electrodeposited into the template to form nanowires that grow from an underlying conductive layer beneath the PAA and extend to the initiation sites of the SWNTs within each pore. In this way, individual vertical channels of SWNTs are created, each with a vertical Pd nanowire back contact. Further Pd deposition results in annular Pd nanoclusters that form on portions of SWNTs extending onto the PAA surface. Two-terminal electrical characteristics produce linear I-V relationships, indicating ohmic contact in the devices.     

Transferring vertically aligned carbon nanotubes onto a polymeric substrate using a hot embossing technique for microfluidic applications

We explored the hot embossing method for transferring vertically aligned carbon nanotubes (CNTs) into microfluidic channels, fabricated on poly-methyl-methacrylate (PMMA). Patterned and unpatterned CNTs were synthesized by microwave plasma-enhanced chemical vapour deposition on silicon to work as a stamp. For hot embossing, 115°C and 1 kN force for 2 min were found to be the most suitable parameters for the complete transfer of aligned CNTs on the PMMA microchannel. Raman and SEM studies were used to analyse the microstructure of CNTs before and after hot embossing. The PMMA microparticles with dimensions (approx. 10 µm in diameter) similar to red blood cells were successfully filtered using laminar flow through these microfluidic channels. Finally, a microfluidic-based point-of-care device for blood filtration and detection of bio-molecules is drawn schematically.     

A method for filling complex polymeric microfluidic devices and arrays

This paper describes an improved method for filling microfluidic structures with aqueous solutions. The method, channel outgas technique (COT), is based on a filling procedure carried out at reduced pressures. This procedure is compared with previously reported methods in which microfluidic channels are filled either by using capillary forces or by applying a pressure gradient at one or more empty reservoirs. The technique has proven to be > 90% effective in eliminating the formation of bubbles within microfluidic networks. It can be applied to many devices, including those containing PDMS-terminated channel features, a single channel inlet, and three-dimensional arrays.