Erik Haroz

Reversible water-solubilization of single-walled carbon nanotubes by polymer wrapping

Abstract Single-walled carbon nanotubes (SWNTs) have been solubilized in water by non-covalently associating them with linear polymers, most successfully with polyvinyl pyrrolidone (PVP) and polystyrene sulfonate (PSS). This association is characterized by tight, uniform association of the polymers with the sides of the nanotubes. A general thermodynamic drive for this wrapping is discussed, wherein the polymer disrupts both the hydrophobic interface with water and the smooth tube–tube interactions in aggregates. The nanotubes can be unwrapped by changing the solvent system. This solubilization process opens the door to solution chemistry on pristine nanotubes, as well as their introduction into biologically relevant systems.

In-plane-aligned membranes of carbon nanotubes

We have produced the first macroscopic objects comprised of highly aligned single-wall carbon nanotubes (SWNTs). These objects are thin membranes prepared by producing a suspension of SWNT segments, introducing the suspension to a strong magnetic field to align the segments, and filtering the suspension in the magnetic field to produce an aligned membrane of SWNT. These membranes exhibited natural cleavage planes parallel to the magnetic field. This preparation of macroscopic samples of aligned single-wall nanotubes permits exploitation of their highly anisotropic properties, and will enable measurement of the electronic, thermal, magnetic, mechanical, and optical properties of bulk nanotube materials.

Role of Surfactants and Salt in Aqueous Two-Phase Separation of Carbon Nanotubes toward Simple Chirality Isolation

Aqueous two-phase extraction has recently been demonstrated as a new method to separate single-wall carbon nanotubes (SWCNTs). In this work, we determined that the mechanism of separation is driven by the hydrophobicity of the surfactant, or combination of surfactants, at the SWCNT surface. This knowledge allowed us to develop a simple approach for obtaining highly enriched single-chirality suspensions in only 1 or 2 steps. These results were obtained by strategically combining multiple surfactants with different diameter-dependent binding affinities for SWCNTs and salts that readjust the surfactant structure within the mixed micelle surrounding the SWCNTs. The procedure is successfully applied to SWCNTs from different sources (CoMoCAT and HiPco) with various diameter distributions (from 0.53 to 1.2 nm). Each separation step is characterized by optical absorption, resonant Raman, and photoluminescence excitation spectroscopies. By determining the SWCNT sorting mechanism, we were able to develop a new set of parameters that separated another chirality.

Dry Contact Transfer Printing of Aligned Carbon Nanotube Patterns and Characterization of Their Optical Properties for Diameter Distribution and Alignment

A scalable and facile approach is demonstrated where as-grown patterns of well-aligned structures composed of single-walled carbon nanotubes (SWNT) synthesized via water-assisted chemical vapor deposition (CVD) can be transferred, or printed, to any host surface in a single dry, room-temperature step using the growth substrate as a stamp. We demonstrate compatibility of this process with multiple transfers for large-scale device and specifically tailored pattern fabrication. Utilizing this transfer approach, anisotropic optical properties of the SWNT films are probed via polarized absorption, Raman, and photoluminescence spectroscopies. Using a simple model to describe optical transitions in the large SWNT species present in the aligned samples, polarized absorption data are demonstrated as an effective tool for accurate assignment of the diameter distribution from broad absorption features located in the infrared. This can be performed on either well-aligned samples or unaligned doped samples, allowing simple and rapid feedback of the SWNT diameter distribution that can be challenging and time-consuming to obtain in other optical methods. Furthermore, we discuss challenges in accurately characterizing alignment in structures of long versus short carbon nanotubes through optical techniques, where SWNT length makes a difference in the information obtained in such measurements. This work provides new insight to the efficient transfer and optical properties of an emerging class of long, large diameter SWNT species typically produced in the CVD process.

Plasmonic Nature of the Terahertz Conductivity Peak in Single-Wall Carbon Nanotubes

Plasmon resonance is expected to occur in metallic and doped semiconducting carbon nanotubes in the terahertz frequency range, but its convincing identification has so far been elusive. The origin of the terahertz conductivity peak commonly observed for carbon nanotube ensembles remains controversial. Here we present results of optical, terahertz, and direct current (DC) transport measurements on highly enriched metallic and semiconducting nanotube films. A broad and strong terahertz conductivity peak appears in both types of films, whose behaviors are consistent with the plasmon resonance explanation, firmly ruling out other alternative explanations such as absorption due to curvature-induced gaps.

Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes.

The one-dimensional character of electrons, phonons and excitons in individual single-walled carbon nanotubes leads to extremely anisotropic electronic, thermal and optical properties. However, despite significant efforts to develop ways to produce large-scale architectures of aligned nanotubes, macroscopic manifestations of such properties remain limited. Here, we show that large (>cm(2)) monodomain films of aligned single-walled carbon nanotubes can be prepared using slow vacuum filtration. The produced films are globally aligned within ±1.5° (a nematic order parameter of ∼1) and are highly packed, containing 1 × 10(6) nanotubes in a cross-sectional area of 1 μm(2). The method works for nanotubes synthesized by various methods, and film thickness is controllable from a few nanometres to ∼100 nm. We use the approach to create ideal polarizers in the terahertz frequency range and, by combining the method with recently developed sorting techniques, highly aligned and chirality-enriched nanotube thin-film devices. Semiconductor-enriched devices exhibit polarized light emission and polarization-dependent photocurrent, as well as anisotropic conductivities and transistor action with high on/off ratios.

Enrichment of Armchair Carbon Nanotubes via Density Gradient Ultracentrifugation: Raman Spectroscopy Evidence

We have used resonant Raman scattering spectroscopy to fully analyze the relative abundances of different (n,m) species in single-walled carbon nanotube samples that are metallically enriched by density gradient ultracentrifugation. Strikingly, the data clearly show that our density gradient ultracentrifugation process enriches the metallic fractions in armchair and near-armchair species. We observe that armchair carbon nanotubes constitute more than 50% of each (2n + m) family.

Coherent Lattice Vibrations in Single-Walled Carbon Nanotubes

We have generated and detected coherent lattice vibrations in single-walled carbon nanotubes corresponding to the radial breathing mode (RBM) using ultrashort laser pulses. Because the band gap is a function of diameter, these RBM-induced diameter oscillations cause ultrafast band gap oscillations, thereby modulating the interband excitonic resonances at the phonon frequencies (3-9 THz). Excitation spectra show a large number of pronounced peaks, allowing the determination of the chiralities present in particular samples and relative population differences of particular chiralities between samples.

Isolation of >1 nm Diameter Single-Wall Carbon Nanotube Species Using Aqueous Two-Phase Extraction

In this contribution we demonstrate the effective separation of single-wall carbon nanotube (SWCNT) species with diameters larger than 1 nm through multistage aqueous two-phase extraction (ATPE), including isolation at the near-monochiral species level up to at least the diameter range of SWCNTs synthesized by electric arc synthesis (1.3-1.6 nm). We also demonstrate that refined species are readily obtained from both the metallic and semiconducting subpopulations of SWCNTs and that this methodology is effective for multiple SWCNT raw materials. Using these data, we report an empirical function for the necessary surfactant concentrations in the ATPE method for separating different SWCNTs into either the lower or upper phase as a function of SWCNT diameter. This empirical correlation enables predictive separation design and identifies a subset of SWCNTs that behave unusually as compared to other species. These results not only dramatically increase the range of SWCNT diameters to which species selective separation can be achieved but also demonstrate that aqueous two-phase separations can be designed across experimentally accessible ranges of surfactant concentrations to controllably separate SWCNT populations of very small (∼0.62 nm) to very large diameters (>1.7 nm). Together, the results reported here indicate that total separation of all SWCNT species is likely feasible by the ATPE method, especially given future development of multistage automated extraction techniques.

Chirality-Selective Excitation of Coherent Phonons in Carbon Nanotubes by Femtosecond Optical Pulses

Using predesigned trains of femtosecond optical pulses, we have selectively excited coherent phonons of the radial breathing mode of specific-chirality single-walled carbon nanotubes within an ensemble sample. By analyzing the initial phase of the phonon oscillations, we prove that the tube diameter initially increases in response to ultrafast photoexcitation. Furthermore, from excitation profiles, we demonstrate that an excitonic absorption peak of carbon nanotubes periodically oscillates as a function of time when the tube diameter undergoes coherent radial breathing mode oscillations.