Magnetic orientation of single-walled carbon nanotubes or their composites using polymer wrapping

Abstract

The magnetic orientation of single-walled carbon nanotubes (SWNTs) or the SWNT composites wrapped with polymer using poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene] (MEHPPV) as the conducting polymer were examined. The formation of SWNT/MEHPPV composites was confirmed by examining absorption and fluorescence spectra. The N,N-dimethylformamide solution of SWNT/MEHPPV composites or the aqueous solution of the shortened SWNTs was introduced dropwise onto a mica or glass plate. The magnetic processing of the composites or the SWNTs was carried out using a superconducting magnet with a horizontal direction (8 T). The AFM images indicated that the SWNT/MEHPPV composites or the SWNTs were oriented randomly without magnetic processing, while with magnetic processing (8 T), they were oriented with the tube axis of the composites or the SWNTs parallel to the magnetic field. In polarized absorption spectra of SWNT/MEHPPV composites on glass plates without magnetic processing, the absorbance due to semiconducting SWNT in the near-IR region in horizontal polarized light was almost the same as that in vertical polarized light. In contrast, with magnetic processing (8 T), the absorbance due to semiconducting SWNT in the horizontal polarization direction against the direction of magnetic field was stronger than that in the vertical polarization direction. Similar results were obtained from the polarized absorption spectra for the shortened SWNTs. These results of polarized absorption spectra also support the magnetic orientation of the SWNT/MEHPPV composites or the SWNTs. On the basis of a comparison of the composites and the SWNTs alone, the magnetic orientation of SWNT/MEHPPV composites is most likely ascribable to the anisotropy in susceptibilities of SWNTs.     

Frequency dependence of the dielectrophoretic separation of single-walled carbon nanotubes

Dielectrophoresis on single-walled carbon nanotubes in surfactant suspensions has been demonstrated to separate metallic from semiconducting tubes by their different electric field-induced polarisabilities. Here we report that the interaction between SWNTs and the surfactant induces a nanotube surface conductance which gives rise to a unique electric field frequency dependence of the dielectrophoretic force acting on semiconducting SWNTs. We observe a surfactant concentration dependent crossover frequency enabling separation of metallic from semiconducting SWNTs at high frequency and deposition of metallic and semiconducting SWNTs at low frequency. Proof for the effectiveness of separation is given by a comparative Raman spectroscopy study on dielectrophoretically deposited tubes excited with two different wavelengths.     

Chiral-angle distribution for separated single-walled carbon nanotubes

Chiral indices (n, m) of metallic and semiconducting single-walled carbon nanotubes (SWNTs) selectively separated via the density-gradient ultracentrifugation process were individually assigned by using an aberration-corrected transmission electron microscope (TEM) operated at 80 kV. Our statistical analysis revealed that armchair (n, n) and chiral (n, n-3) SWNTs with large chiral angles (>20 degrees) are dominant metallic nanotubes in the separated samples, whereas such a noticeable preference of particular indices was not observed for semiconducting nanotubes. Some significant discrepancies were found between the TEM and spectroscopic results on the major chiral indices and the metal/semiconductor ratios in these SWNTs.     

Simultaneous dielectrophoretic separation and assembly of single-walled carbon nanotubes on multigap nanoelectrodes and their thermal sensing properties

By using the specifically designed multigap nanoelectrodes, we demonstrated an effective approach for the simultaneous dielectrophoretic separation and assembly of metallic and semiconducting single-walled carbon nanotubes (SWNTs). An approximate metallic-semiconducting-metallic multiarray structure was created by an inward-propagative sequential assembly of SWNTs under ac electric field. Such kinds of SWNT multiarray structures exhibited ultra-low-power consumption and excellent thermal sensing performances with the sensitivity being dependent on the number of gaps: the more gaps, the higher sensitivity. The effective separation of metallic and semiconducting tubes in different gaps is believed to be responsible for the improved sensitivity to temperature.     

Diameter‐ and Metallicity‐Selective Enrichment of Single‐Walled Carbon Nanotubes Using Polymethacrylates with Pendant Aromatic Functional Groups

Current methods for the synthesis of single‐walled nanotubes (SWNTs) produce mixtures of semiconducting (sem‐) and metallic (met‐) nanotubes. Most approaches to the chemical separation of sem‐/met‐SWNTs are based on small neutral molecules or conjugated aromatic polymers, which characteristically have low separation/dispersion efficiencies or present difficulties in the postseparation removal of the polymer so that the resulting field‐effect transistors (FETs) have poor performance. In this Full Paper, the use of three polymethacrylates with different pendant aromatic functional groups to separate cobalt–molybdenum catalyst (CoMoCAT) SWNTs according to their metallicity and diameters is reported. UV/Vis/NIR spectroscopy indicates that poly(methyl‐methacrylate‐co‐fluorescein‐o‐acrylate) (PMMAFA) and poly(9‐anthracenylmethyl‐methacrylate) (PAMMA) preferentially disperse semiconducting SWNTs while poly(2‐naphthylmethacrylate) (PNMA) preferentially disperses metallic SWNTs, all in dimethylforamide (DMF). Photoluminescence excitation (PLE) spectroscopy indicates that all three polymers preferentially disperse smaller‐diameter SWNTs, particularly those of (6,5) chirality, in DMF. When chloroform is used instead of DMF, the larger‐diameter SWNTs (8,4) and (7,6) are instead selected by PNMA. The solvent effects suggest that diameter selectivity and change of polymer conformation is probably responsible. Change of the polymer fluorescence upon interaction with SWNTs indicates that metallicity selectivity presumably results from the photon‐induced dipole–dipole interaction between polymeric chromophore and SWNTs. Thin‐film FET devices using semiconductor‐enriched solution with PMMAFA have been successfully fabricated and the device performance confirms the sem‐SWNTs enrichment with a highly reproducible on/off ratio of about 10³.     

Electronic‐Type‐ and Diameter‐Dependent Reduction of Single‐Walled Carbon Nanotubes Induced by Adsorption of Electron‐Donor Molecules

The adsorption of the organic donor molecules tetrakis(dimethylamino)ethylene (TDAE) and cobaltocene (CoCp₂) on high‐pressure CO decomposition (HiPco) single‐walled carbon nanotubes (SWNTs) is investigated using density functional theory (DFT), optical absorption, and Raman spectra methods. The selective reduction of SWNTs according to the electronic type and diameter of SWNTs is revealed. The reduction rate decreases in the order: metallic SWNTs ≥ large‐diameter semiconducting SWNTs > small‐diameter semiconducting SWNTs.     

Transition of single-walled carbon nanotubes from metallic to semiconducting in field-effect transistors by hydrogen plasma treatment

We report hydrogen plasma treatment results on converting the metallic single-walled carbon nanotubes to semiconducting single-walled carbon nanotubes. We found that the as-grown single-walled carbon nanotubes (SWNTs) can be sorted as three groups which behave as metallic, as-metallic, and semiconducting SWNTs. These three groups have different changes under hydrogen plasma treatment and successive annealing process. The SWNTs can be easily hydrogenated in the hydrogen plasma environment and the as-metallic SWNTs can be transformed to semiconducting SWNTs. The successive annealing process can break the C-H bond, so the conversion is reversible.     

Alignment of SWNTs by protein-ligand interaction of functionalized magnetic particles under low magnetic fields

Carbon nanotubes (CNTs) have attracted considerable attention for applications using their superior mechanical, thermal and electrical properties. A simple method to controllably align single-walled CNTs (SWNTs) by using magnetic particles embedded with superparamagnetic iron oxide as an accelerator under the magnetic field was developed. The functionalization of SWNTs using biotin, interacted with streptavidin-coupled magnetic particles (micro-to-nano in diameter), and layer-by-layer assembly were performed for the alignment of a particular direction onto the clean silicon and the gold substrate at very low magnetic forces (0.02-0.89 T) at room temperature. The successful alignment of the SWNTs with multi-layer film was observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). By changing the orientation and location of the substrates, crossed-networks of SWNTs-magnetic particle complex could easily be fabricated. We suggest that this approach, which consists of a combination of biological interaction among streptavidin-biotin and magnetite particles, should be useful for lateral orientation of individual SWNTs with controllable direction.     

Voltage-induced dependence of Raman-active modes in single-wall carbon nanotube thin films

We report on electrical Raman measurements in transparent and conducting single-wall carbon nanotube (SWNT) thin films. Application of external voltage results in downshifts of the D and G modes and in reduction of their intensity. The intensities of the radial breathing modes increase with external electric field related to the application of the external voltage in metallic SWNTs, while decreasing in semiconducting SWNTs. A model explaining the phenomenon in terms of both direct and indirect (Joule heating) effects of the field is proposed. Our work rules out the elimination of large amounts of metallic SWNTs in thin film transistors using high field pulses. Our results support the existence of Kohn anomalies in the Raman-active optical branches of metallic graphitic materials.     

Preferential syntheses of semiconducting vertically aligned single-walled carbon nanotubes for direct use in FETs

We have combined fast heating with plasma enhanced chemical vapor deposition (PECVD) for preferential growth of semiconducting vertically aligned single-walled carbon nanotubes (VA-SWNTs). Raman spectroscopic estimation indicated a high yield of up to 96% semiconducting SWNTs in the VA-SWNT array. The as-synthesized semiconducting SWNTs can be used directly for fabricating FET devices without the need for any postsynthesis purification or separation.     

The synergistic effect of nanocrystal integration and process optimization on solar cell efficiency

This paper investigates the roles of semiconducting single-walled carbon nanotubes (SWNTs) and metallic SWNTs in the SWNT/poly(3-hexylthiophene) (P3HT)-based photovoltaic conversion system. SWNTs containing different fractions of semiconducting nanotubes were conjugated with P3HT by virtue of π-π interaction. The energy transfer and carrier transport mechanisms in the photovoltaic composites were experimentally investigated by optical absorption spectroscopy, photoluminescence spectroscopy and carrier mobility measurements. At low loading of SWNTs, a high percentage of semiconducting nanotubes result in diminished non-radiative decay of exciton and lower carrier mobility, causing higher open circuit voltage and lower photocurrent. At an optimized morphology, SWNT/P3HT/phenyl-C61-butyric acid methyl ester (PCBM) hybrid-based solar cells demonstrated much higher photocurrent than a reference solar cell (P3HT:PCBM) due to the improved carrier mobility. Further thermal annealing of the devices significantly increased the open circuit voltage to 610?mV, resulting in an 80% increase of power conversion efficiency in comparison to the reference solar cell. These results are expected to lay a foundation for the integration of various nanocrystals into solar cells for efficient photovoltaic conversion.     

Prolonging charge separation in P3HT-SWNT composites using highly enriched semiconducting nanotubes

Single-walled carbon nanotubes (SWNTs) have potential as electron acceptors in organic photovoltaics (OPVs), but the currently low-power conversion efficiencies of devices remain largely unexplained. We demonstrate effective redispersion of isolated, highly enriched semiconducting and metallic SWNTs into poly(3-hexylthiophene) (P3HT). We use these enriched blends to provide the first experimental evidence of the negative impact of metallic nanotubes. Time-resolved microwave conductivity reveals that the long-lived carrier population can be significantly increased by incorporating highly enriched semiconducting SWNTs into semiconducting polymer composites.     

Graphene oxides for homogeneous dispersion of carbon nanotubes

Graphene oxides (GOs) in terms of both structure and property are essentially polyelectrolytes in a two-dimensional sheet configuration. As is well-established in the literature, polyelectrolytes are, in general, good dispersion agents for single-walled carbon nanotubes (SWNTs), which are otherwise in bundles because of strong van der Waals interactions. We report here a study in which GOs were used to disperse SWNTs, both as-purified and separated semiconducting SWNTs, for solution-like homogeneous suspensions. As a demonstration for their potentials, the optically transparent dispersions were used in a more accurate determination of the absorptivities for the band-gap transitions in semiconducting SWNTs. Results on exploration of the use of the GO-dispersed SWNTs in the development of unique carbon nanocomposite materials are also presented and discussed.     

Sorting carbon nanotubes by electronic structure using density differentiation

The heterogeneity of as-synthesized single-walled carbon nanotubes (SWNTs) precludes their widespread application in electronics, optics and sensing. We report on the sorting of carbon nanotubes by diameter, bandgap and electronic type using structure-discriminating surfactants to engineer subtle differences in their buoyant densities. Using the scalable technique of density-gradient ultracentrifugation, we have isolated narrow distributions of SWNTs in which >97% are within a 0.02-nm-diameter range. Furthermore, using competing mixtures of surfactants, we have produced bulk quantities of SWNTs of predominantly a single electronic type. These materials were used to fabricate thin-film electrical devices of networked SWNTs characterized by either metallic or semiconducting behaviour.     

Selective etching of metallic single-wall carbon nanotubes with hydrogen plasma

We present Raman scattering and scanning tunnelling microscopy (STM) measurements on hydrogen plasma etched single-wall carbon nanotubes (SWNTs). Interestingly, both the STM and Raman spectroscopy show that the metallic SWNTs are dramatically altered and highly defected by the plasma treatment. In addition, structural characterizations show that metal catalysts are detached from the ends of the SWNT bundles. For semiconducting SWNTs we observe no feature of defects or etching along the nanotubes. Raman spectra in the radial breathing mode region of plasma-treated SWNT material show that most of the tubes are semiconducting. These results show that hydrogen plasma treatment favours etching of metallic nanotubes over semiconducting ones and therefore could be used to tailor the electronic properties of SWNT raw materials.     

Enrichment of (8,4) Single‐Walled Carbon Nanotubes Through Coextraction with Heparin

Heparin sodium salt is investigated as a dispersant for dispersing single‐walled carbon nanotubes (SWNTs). Photoluminescence excitation (PLE) spectroscopy is used for identification and abundance estimation of the chiral species. It is found that heparin sodium salt preferentially disperses larger‐diameter Hipco SWNTs. When used to disperse CoMoCAT nanotube samples, heparin has a strong preference for (8,4) tubes, which have larger diameter than the predominant (6,5) in pristine CoMoCAT samples. PLE intensity due to (8,4) tubes increases from 7% to 60% of the total after threefold extractions. Computer modeling verifies that the complex of (8,4) SWNTs and heparin has the lowest binding energy amongst the four semiconducting species present in CoMoCAT. Network field‐effect transistors are successfully made with CoMoCAT/heparin and CoMoCAT/sodium dodecylbenzene sulfonate (SDBS)–heparin (x3), confirming the easy removability of heparin.     

Single-walled carbon nanotubes under the influence of dynamic coordination and supramolecular chemistry

A dynamic coordinative-directed solubilization of single-walled carbon nanotubes (SWNTs) in aqueous solutions has been achieved through a combination of a Zn(II) metalloporphyrin complex and a cis-protected Pd(II) complex, which are believed to form charged acyclic and/or cyclic adducts on or around the side walls of SWNTs. The solubilization of SWNTs in aqueous solution only occurs when these acyclic and/or cyclic complexes are allowed to enter simultaneously into a self-assembly process with SWNTs under mild conditions. The aqueous solubility properties that these dynamic complexes confer upon SWNTs are believed to involve noncovalent bonding interactions between the two entities. They have been probed in solution using ultraviolet and visible absorption spectroscopy and in thin films using high-resolution transmission electron microscopy. The supramolecular electronic effects that the individual components of their acyclic and/or cyclic complexes impart upon a single semiconducting SWNT have been probed within a nanotube field-effect transistor device.     

Individual single-walled carbon nanotubes as nanoelectrodes for electrochemistry

We demonstrate the use of individual single-walled carbon nanotubes (SWNTs) as nanoelectrodes for electrochemistry. SWNTs were contacted by nanolithography, and cyclic voltammetry was performed in aqueous solutions. Interestingly, metallic and semiconducting SWNTs yielded similar steady-state voltammetric curves. We clarify this behavior through a model that considers the electronic structure of the SWNTs. Interfacial electron transfer to the SWNTs is observed to be very fast but can nonetheless be resolved due to the nanometer critical dimension of SWNTs. These studies demonstrate the potential of using a SWNT as a model carbon nanoelectrode for electrochemistry.     

Why semiconducting single-walled carbon nanotubes are separated from their metallic counterparts

The separation of single-walled carbon nanotubes (SWNTs) according to their electronic structure has attracted much recent attention. In many cases, metallic SWNTs are separated from semiconducting SWNTs and enriched in the supernatant due to stronger interaction between metallic SWNTs and adsorbates. However, the inverse separation of semiconducting from metallic SWNTs is often observed. In this computational study, the underlying mechanism is elucidated by density functional theory. We show that the shape of an aromatic molecule, the degree of hybridization between a molecule and a SWNT, and the oxidative state of SWNTs can affect the type of enriched SWNTs. In principle, one can control the type of enriched SWNTs by selecting a structurally compatible aromatic molecule or changing the hole concentration of the SWNTs.     

The evaluation of individual dispersion of single-walled carbon nanotubes using absorption and fluorescence spectroscopic techniques

We have investigated the degree of dispersion of single-walled carbon nanotubes (SWNTs) in solution using laser spectroscopic techniques. SWNTs were suspended in aqueous media using a sodium dodecyl sulfate (SDS) surfactant. SWNTs with different dispersion states were prepared by controlling the intensity and duration of sonication and centrifugation. The absorption and fluorescence spectroscopic techniques were employed to characterize the different dispersion state of the prepared samples. Nanotube suspensions with better dispersion showed higher fluorescence and sharper absorption peaks. The fluorescence data were characterized as a function of the nanotube chirality, and absorption peak shifts were analyzed depending on the first and second van Hove singularities (vHs) of semiconducting nanotubes.