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.     

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.     

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.     

Magnetic nanoparticle-based separation of metallic and semiconducting carbon nanotubes

We report a simple and scalable method for the separation of semiconducting single-walled carbon nanotubes (SWNTs) from metallic SWNTs using magnetic nanoparticles (MNPs) functionalized with polycationic tri-aminated polysorbate 80 (TP80). MNPs-TP80 are selectively adsorbed on acid-treated semiconducting SWNTs, which makes the semiconducting SWNTs be highly concentrated to over 95% under a magnetic field. Almost all the field effect transistor network devices, which were fabricated using separated semiconducting SWNTs, exhibited a p-type semiconducting behavior with an on/off ratio of higher than 10(4).     

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.     

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.     

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.     

Selective suspension in aqueous sodium dodecyl sulfate according to electronic structure type allows simple separation of metallic from semiconducting single-walled carbon nanotubes

Both density gradient centrifugation and gel electrophoresis have been reported to allow high throughput separation of metallic from semiconducting single-walled carbon nanotubes (SWNTs) when using aqueous sodium dodecyl sulphate (SDS) suspensions. We show here that both methods rely on an initial dispersion-by-sonication step, which is already selective with respect to electronic structure type. The corresponding aqueous SDS “starting” suspensions obtained after sonication and purification by simple centrifugation (70,000 g, 1 h) contain semiconducting SWNTs primarily in the form of small bundles whereas metallic SWNTs are predominantly suspended as individual tubes. Density gradient centrifugation then separates the bundles from the individual tubes on the basis of differences in their overall buoyant densities. Gel electrophoresis separates the longer bundles from the shorter individual tubes on the basis of their different mobilities. We also demonstrate that such starting suspensions can be fractionated according to electronic structure type by even simpler techniques such as size exclusion chromatography or gel filtration, thus opening the way for simple scale-up.      

Resonance Raman spectroscopy characterization of single-wall carbon nanotube separation by their metallicity and diameter

Several techniques were recently reported for the bulk separation of metallic (M) and semiconducting (S) single wall carbon nanotubes (SWNTs), using optical absorption and resonance Raman spectroscopy (RRS) as a proof of the separation. In the present work, we develop a method for the quantitative evaluation of the M to S separation ratio, and also for the SWNT diameter selectivity of the separation process, based on RRS. The relative changes in the integrated intensities of the radial-breathing mode (RBM) features, with respect to the starting material, yield the diameter probability distribution functions for M and S SWNTs in the separated fractions, accounting for the different resonance conditions of individual SWNTs, while the diameter distribution of the starting material is obtained following the fitting procedure developed by Kuzmany and coworkers. Features other than the RBM are generally less effective for characterization of the separation process for SWNTs.     

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.