Carbon nanotube-polymer nanocomposite infrared sensor

The infrared photoresponse in the electrical conductivity of single-walled carbon nanotubes (SWNTs) is dramatically enhanced by embedding SWNTs in an electrically and thermally insulating polymer matrix. The conductivity change in a 5 wt % SWNT-polycarbonate nanocomposite is significant (4.26%) and sharp upon infrared illumination in the air at room temperature. While the thermal effect predominates in the infrared photoresponse of a pure SWNT film, the photoeffect predominates in the infrared photoresponse of SWNT-polycarbonate nanocomposites.     

Assessment of the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes

Scanning electrochemical microscopy (SECM) has been employed in the feedback mode to assess the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes (SWNTs). It is shown that, even though the network comprises both metallic and semiconducting SWNTs, at high density (well above the percolation threshold for metallic SWNTs) and with approximately millimolar concentrations of redox species the network behaves as a thin metallic film, irrespective of the formal potential of the redox couple. This result is particularly striking since the fractional surface coverage of SWNTs is only approximately 1% and SECM delivers high mass transport rates to the network. Finite element simulations demonstrate that under these conditions diffusional overlap between neighboring SWNTs is significant so that planar diffusion prevails in the gap between the SECM tip and the underlying SWNT substrate. The SECM feedback response diminishes at higher concentrations of the redox species. However, wet gate measurements show that at the solution potentials of interest the conductivity is sufficiently high that lateral conductivity is not expected to be limiting. This suggests that reaction kinetics may be a limiting factor, especially since the low surface coverage of the SWNT network results in large fluxes to the SWNTs, which are characterized by a low density of electronic states. For electroanalytical purposes, significantly, two-dimensional SWNT networks can be considered as metallic films for typical millimolar concentrations employed in amperometry and voltammetry. Moreover, SWNT networks can be inexpensively and easily formed over large scales, opening up the possibility of further electroanalytical applications.     

The effects of CNT alignment on electrical conductivity and mechanical properties of SWNT/epoxy nanocomposites

The single-walled carbon nanotubes (SWNTs) filled nanocomposite SWNT/epoxy resin composite with good uniformity, dispersion and alignment of SWNTs and with different SWNTs concentrations was produced by solution casting technique. Subsequently, the semidried mixture was stretched repeatedly along one direction at a large draw-ratio of 50 for 100 times at ambient atmosphere manually to achieve a good alignment and to promote dispersion of SWNTs in the composite matrix. Composite showed higher electrical conductivities and mechanical properties such as the Young’s modulus and tensile strength along the stretched direction than perpendicular to it, and the electrical property of composite rise with the increase of SWNT concentration. The percolation threshold value of electrical conductivity along the stretching direction is lower than the value perpendicular to the SWNTs orientation. In addition, the anisotropic electric and mechanical properties results, SEM micrograph and the polarized Raman spectra of the SWNT/epoxy composite reveal that SWNTs were well dispersed and aligned in the composites by the repeated stretching process.     

Transparent conductive thin film synthesis based on single-walled carbon nanotubes dispersion containing polymethylmethacrylate binder

Transparent conductive hybrid thin films of single-walled carbon nanotubes (SWNTs) and polymethyl methacrylate (PMMA) are fabricated using dispersions containing SWNTs and water-borne PMMA binder. The polymer binder was used as adhesion promoter between the SWNTs and the substrate. The polymer binder content in the SWNTs dispersion is varied to obtain the optimum optical transmittance, electrical conductivity, and mechanical adhesion. The PMMA and SWNT network formed the composite over substrate. The fabricated SWNTs/PMMA hybrid films are immersed in nitric acid (HNO3) and thionyl chloride (SOCl2) to improve electrical conductivity. SWNTs films with 0.2-0.6 mg/ml polymer binder have sheet resistance of 80-140 ohms/sq at a transmittance of about 80% and a strong adhesion on glass substrate. Furthermore, the electrical stability of the films is improved via the PMMA addition. This results indicates that the SWNTs/PMMA hybrid films fabricated by this method can be used as an alternative of indium tin oxide (ITO) film on flexible substrate.     

Computational modeling of the thermal conductivity of single-walled carbon nanotube-polymer composites

A computational model was developed to study the thermal conductivity of single-walled carbon nanotube (SWNT)-polymer composites. A random walk simulation was used to model the effect of interfacial resistance on the heat flow in different orientations of SWNTs dispersed in the polymers. The simulation is a modification of a previous model taking into account the numerically determined thermal equilibrium factor between the SWNTs and the composite matrix material. The simulation results agreed well with reported experimental data for epoxy and polymethyl methacrylate (PMMA) composites. The effects of the SWNT orientation, weight fraction and thermal boundary resistance on the effective conductivity of composites were quantified. The present model is a useful tool for the prediction of the thermal conductivity within a wide range of volume fractions of the SWNTs, so long as the SWNTs are not in contact with each other. The developed model can be applied to other polymers and solid materials, possibly even metals.     

Evaluation of SOCl2 doping effect on electrical conductivity of thin films of SWNTs and SWNT/PEDOT-PSS composites

Transparent conductive thin films of single-walled carbon nanotubes (SWNTs) and their nanocomposites with an organic conductive polymer, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) with different CNT loadings ranging from 20 to 90 wt% were prepared and doped by exposing them to thionyl chloride (SOCl2) vapors. After exposure to SOCl2 vapor for 1 h, the SWNT film showed about 15-18% increase of electrical conductivity, while on the other hand pristine polymer film showed a decrease of electrical conductivity. The SWNT-polymer composite films showed a drastic increase in conductivity by doping with SOCl2 vapor, most interestingly, the doping effect was much higher for composite films with less CNT weight fraction and it was linearly decreased with increasing CNT loading. For instance, composite film with 10% and 90% CNT loading demonstrated about 65% and 10% increase of electrical conductivity, respectively. The interaction of SOCl2 vapors on SWNTs and composite films is investigated by UV-visible absorption and Raman spectroscopy.     

Properties of well aligned SWNT modified poly (methyl methacrylate) nanocomposites

The PMMA/SWNT composites with good uniformity, dispersion and alignment of SWNT were fabricated in a stretching process. The semidried mixture was stretched along one direction at a draw ratio of 50 before it was dried, and then folded along the same direction stretching repeatedly for 100 times. The TEM and SEM observation demonstrated that SWNT in the PMMA/SWNT composite tend to align in the stretching direction. The electrical conductivity and the mechanical properties of composite rise with the increase of SWNT concentration, composite films showed higher conductivity and higher mechanical draw ratios along the stretched direction than perpendicular to it. The TGA revealed that embedding the SWNTs into the PMMA matrix also improves the thermal stability of the composite.     

Anisotropic properties of aligned SWNT modified poly (methyl methacrylate) nanocomposites

The poly (methyl methacrylate) (PMMA)/single-walled carbon nanotube (SWNT) composites with good uniformity, dispersion and alignment of SWNT were fabricated in an improved figuration process. The semidried mixture was stretched along one direction at a drawing ratio of 50 before it was dried, and then folded along the same direction stretching repeatedly for 100 times. The transmission electron microscopic (TEM) observation demonstrated that SWNT in the PMMA/SWNT composite tends to align in the stretching direction owing to a torque exerting on it in the stretching process. The electrical and mechanical properties of PMMA/SWNT composite were studied as a function of SWNT orientation and concentration. The aligned SWNT modified PMMA/SWNT composite presented highly anisotropic properties. The experimental results showed that the electrical conductivity and mechanical properties of composite rise with the increase of SWNT concentration, and that composite films showed higher conductivity and higher mechanical draw ratios along the stretched direction than perpendicular to it. The thermogravimetric analysis (TGA) revealed that embedding the SWNTs into the PMMA matrix also improves the thermal stability of the composite.     

Detection of a nerve agent simulant using single-walled carbon nanotube networks: dimethyl-methyl-phosphonate

Single-walled carbon nanotube (SWNT) networks were used to detect hazardous dimethyl-methyl-phosphonate (DMMP) gas in real time, employing two different metals as electrodes. Random networks of SWNTs were simply obtained by drop-casting a SWNT-containing solution onto a surface-oxidized Si substrate. Although the electrical responses to DMMP at room temperature were reversible for both metals, the Pd-contacting SWNT network sensors exhibited a higher response and a shorter response time than those of the Au-contacting SWNT network sensors at the same DMMP concentration, due to the stronger interactions between the SWNTs and Pd surface atoms. In Pd-contacting SWNT network sensors, the response increased linearly with increasing DMMP concentration and reproducible response curves were obtained for DMMP levels as low as 1 ppm. These results indicate that SWNT networks in contact with Pd electrodes can function as good DMMP sensors at room temperature with scalable and fast response and excellent recovery.     

Controlled growth and characterization of two-dimensional single-walled carbon-nanotube networks for electrical applications

We demonstrate the reproducible fabrication of single-walled carbon nanotube (SWNT) networks, via catalyzed chemical vapor deposition (cCVD). Fe nanoparticles are employed as the catalyst, with methane as the carbon-containing gas. cCVD growth under these conditions results in the formation of multiply interconnected, random, two-dimensional networks of SWNTs. Investigation of the effect of parameters such as methane flow rate and temperature on the growth process enables control over the density of the network, which controls the network conductivity. Low-density networks demonstrate p-type semiconductor behavior, whilst high-density networks exhibit semimetallic behavior. In both cases conductance is demonstrated over macroscopic length scales, up to millimeters, much longer than the individual SWNTs, despite the surface coverage being <1 %. The networks can be defined in regions of a surface by photolithography before or after growth. Controlled growth of SWNT networks thus enables the application of SWNTs as macroscale conductors with controllable, predictable, and reproducible characteristics.     

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.     

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.     

Reducing electrical resistance in single-walled carbon nanotube networks: effect of the location of metal contacts and low-temperature annealing

The ability to control the density of single-walled carbon nanotubes (SWNTs) during the formation of 2D networks allows one to tune the electrical properties of these thin-films from semiconductive to metallic conduction, allowing their use in numerous new materials applications. However, the resistances of such thin-films are generally non-optimal, dominated by the effects of inter-SWNT tunneling junctions, metal/SWNT contacts, sidewall defects, and the presence of residual dopants. These studies provide insight into the relative contributions of these various items to the overall resistance of an SWNT network contacted by Ti electrodes, and ways to reduce these effects via changing the structure of the metal/SWNT contact, and annealing at low temperature. Further, the addition of a mild-acid treatment was found to cause a 13-fold reduction in resistance and much greater reproducibility in inter-network conductivity.     

Nano Chemical Sensors With Polymer-Coated Carbon Nanotubes

A simple sensor platform consisting of an interdigitated electrode (IDE) pattern has been fabricated for sensing gas and organic vapors. Purified single-walled carbon nanotubes (SWNTs) in the form of a network laid on the IDE by solution casting serve as the sensor material. The electrical conductivity of the SWNT network changes reproducibly upon exposure to various gases and vapors. Selectivity to specific gases, for example, chlorine and hydrochloric acid vapor, is demonstrated by coating the SWNTs with polymers such as chlorosulfonated polyethylene and hydroxypropyl cellulose.     

Nanoscale Charge Percolation Analysis in Polymer‐Sorted (7,5) Single‐Walled Carbon Nanotube Networks

The current percolation in polymer‐sorted semiconducting (7,5) single‐walled carbon nanotube (SWNT) networks, processed from solution, is investigated using a combination of electrical field‐effect measurements, atomic force microscopy (AFM), and conductive AFM (C‐AFM) techniques. From AFM measurements, the nanotube length in the as‐processed (7,5) SWNTs network is found to range from ≈100 to ≈1500 nm, with a SWNT surface density well above the percolation threshold and a maximum surface coverage ≈58%. Analysis of the field‐effect charge transport measurements in the SWNT network using a 2D homogeneous random‐network stick‐percolation model yields an exponent coefficient for the transistors OFF currents of 16.3. This value is indicative of an almost ideal random network containing only a small concentration of metallic SWNTs. Complementary C‐AFM measurements on the other hand enable visualization of current percolation pathways in the xy plane and reveal the isotropic nature of the as‐spun (7,5) SWNT networks. This work demonstrates the tremendous potential of combining advanced scanning probe techniques with field‐effect charge transport measurements for quantification of key network parameters including current percolation, metallic nanotubes content, surface coverage, and degree of SWNT alignment. Most importantly, the proposed approach is general and applicable to other nanoscale networks, including metallic nanowires as well as hybrid nanocomposites.     

Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes

We present a rational and general method to fabricate a high-densely packed and aligned single-walled carbon-nanotube (SWNT) material by using the zipping effect of liquids to draw tubes together. This bulk carbon-nanotube material retains the intrinsic properties of individual SWNTs, such as high surface area, flexibility and electrical conductivity. By controlling the fabrication process, it is possible to fabricate a wide range of solids in numerous shapes and structures. This dense SWNT material is advantageous for numerous applications, and here we demonstrate its use as flexible heaters as well as supercapacitor electrodes for compact energy-storage devices.     

Methods for enhanced control over the density and electrical properties of SWNT networks

The formation of manufacturable electronic materials that incorporate single-walled carbon nanotubes (SWNTs) will most likely involve the use of networks of these molecular wires, due to the enhanced current drive and reproducibility of such films. Therefore, control over the density of SWNTs during the deposition of 2-D networks is of critical importance for the development of numerous enhanced electronic materials. Room temperature deposition methods are of particular interest as they allow separation, purification, and/or chemical modification of SWNTs before deposition. This article reports three iterative liquid-deposition techniques that allow control over the properties of three distinct types of SWNT networks. First, density control was obtained for 2-D networks of unbundled, high-aspect ratio SWNTs. Such networks exhibited semiconductive behavior, with tunable on/off ratios. Second, electrically continuous 2-D clusters of high aspect ratio SWNTs were formed by allowing capillary forces to develop in a sessile suspension droplet. These constructs displayed tunable metallic conductivity, and may have the applications as interconnects in microelectronics. Finally, highly conductive, 3-D networks of bundled SWNTs were formed via an evaporation method. For these three types of networks, the density of SWNTs, and thus the macroscopic conductance, was readily controlled via the number of deposition cycles used in their formation.     

Colored semitransparent conductive coatings consisting of monodisperse metallic single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) are promising materials for transparent conduction as a result of their exceptional electrical, optical, mechanical, and chemical properties. However, since current synthetic methods yield polydisperse mixtures of SWNTs, the performance of SWNT transparent conductive films has previously been hindered by semiconducting species. Here, we describe the performance of transparent conductors produced using predominantly metallic SWNTs. Compared with unsorted material, films enriched in metallic SWNTs can enhance conductivity by factors of over 5.6 in the visible and 10 in the infrared. Moreover, by using monodisperse metallic SWNTs sorted with angstrom-level resolution in diameter, semitransparent conductive coatings with tunable optical transmittance can be produced.     

Fabrication and characterization of single walled nanotube supercapacitor electrodes with uniform pores using electrophoretic deposition

Well dispersed aqueous suspensions containing single walled carbon nanotubes (SWNTs) were prepared without surfactants by functionalizing SWNTs in an acid treatment. SWNT coated electrodes were prepared from the SWNT aqueous suspensions using various methods to create uniform nanoporous networks of SWNTs on stainless steel (SST) current collectors. The EPD process was identified as the primary tool for reliably producing uniform SWNT nanoporous networks on SST substrates. Optical and scanning electron microscopic images and the BET surface area analysis were used to evaluate the SWNT dispersion quality of the electrodes. The average SWNT nanopore size produced from the EPD process was found about 1 nm and was nearly unaffected by extended EPD processing times. The SWNT coated electrodes were characterized using the cyclic voltammetry and their capacitance was determined. A correlation between the extended EPD processing time and the electrode capacitance was quantified.     

Single-walled carbon nanotube thermopile for broadband light detection

We designed a thermopile based on a PN doping profile engineered in a suspended film of single-walled carbon nanotubes (SWNTs). Using estimates of the film local Seebeck coefficients, the SWNT thermopile was optimized in situ through depositions of potassium dopants. The overall performances of the thermopile were found to be comparable to state-of-the-art SWNT bolometers. The device is characterized at room temperature by a time response of 36 ms, typical of thermal detectors, and an optimum spectral detectivity of 2 × 10(6) cm Hz(1/2)/W in the visible and near-infrared. This paper presents the first thermopile made of a suspended SWNT film and paves the way to new applications such as broadband light (including THz) detection and thermoelectric power generation.