Dielectric Screening inside Carbon Nanotubes.

Dielectric screening plays a vital role in determining physical properties at the nanoscale and affects our ability to detect and characterize nanomaterials using optical techniques. We study how dielectric screening changes electromagnetic fields and many-body effects in nanostructures encapsulated inside carbon nanotubes. First, we show that metallic outer walls reduce the scattering intensity of the inner tube by 2 orders of magnitude compared to that of air-suspended inner tubes, in line with our local field calculations. Second, we find that the dielectric shift of the optical transition energies in the inner walls is greater when the outer tube is metallic than when it is semiconducting. The magnitude of the shift suggests that the excitons in small-diameter inner metallic tubes are thermally dissociated at room temperature if the outer tube is also metallic, and in essence, we observe band-to-band transitions in thin metallic double-walled nanotubes.

Nanomechanical Spectroscopy of 2D Materials.

We introduce a nanomechanical platform for fast and sensitive measurements of the spectrally resolved optical dielectric function of 2D materials. At the heart of our approach is a suspended 2D material integrated into a high Q silicon nitride nanomechanical resonator illuminated by a wavelength-tunable laser source. From the heating-related frequency shift of the resonator as well as its optical reflection measured as a function of photon energy, we obtain the real and imaginary parts of the dielectric function. Our measurements are unaffected by substrate-related screening and do not require any assumptions on the underling optical constants. This fast (τrise ∼ 135 ns), sensitive (noise-equivalent power = 90⁣pW√Hz), and broadband (1.2-3.1 eV, extendable to UV-THz) method provides an attractive alternative to spectroscopic or ellipsometric characterization techniques.

Moiré-Induced Vibrational Coupling in Double-Walled Carbon Nanotubes.

Moiré patterns are additional, long-range periodicities in twisted crystalline bilayers. They are known to fundamentally change the electronic states of the layers, but similar effects on their mechanical and vibrational properties have not been discussed so far. Here we show that the moiré potential shifts the radial breathing mode in double-walled carbon nanotubes (DWCNTs). The change in frequency is expected to be proportional to the shift in optical transition energies, which are induced by the moiré patterns. To verify our model, we performed resonance Raman scattering on purified and sorted semiconducting DWCNTs. We find that the radial breathing mode shifts up to 14 cm-1 higher in energy followed by displacement of optical transition energies of up to 200 meV to lower energies, in comparison to the single-walled tubes. We show how to identify the strong coupling condition in DWCNTs from their phonon frequencies and construct a Kataura plot to aid their future experimental assignment.

Anti-Stokes Raman Scattering of Single Carbyne Chains.

We investigate the anti-Stokes Raman scattering of single carbyne chains confined inside double-walled carbon nanotubes. Individual chains are identified using tip-enhanced Raman scattering (TERS) and heated by resonant excitation with varying laser powers. We study the temperature dependence of carbyne's Raman spectrum and quantify the laser-induced heating based on the anti-Stokes/Stokes ratio. Due to its molecular size and its large Raman cross section, carbyne holds great promise for local temperature monitoring, with potential applications ranging from nanoelectronics to biology.

Surface-Enhanced Raman Scattering and Surface-Enhanced Infrared Absorption by Plasmon Polaritons in Three-Dimensional Nanoparticle Supercrystals.

Surface-enhanced vibrational spectroscopy strongly increases the cross section of Raman scattering and infrared absorption, overcoming the limited sensitivity and resolution of these two powerful analytic tools. While surface-enhanced setups with maximum enhancement have been studied widely in recent years, substrates with reproducible, uniform enhancement have received less attention although they are required in many applications. Here, we show that plasmonic supercrystals are an excellent platform for enhanced spectroscopy because they possess a high density of hotspots in the electric field. We describe the near field inside the supercrystal within the framework of plasmon polaritons that form due to strong light-matter interaction. From the polariton resonances we predict resonances in the far-field enhancement for Raman scattering and infrared absorption. We verify our predictions by measuring the vibrations of polystyrene molecules embedded in supercrystals of gold nanoparticles. The intensity of surface-enhanced Raman scattering is uniform within 10% across the crystal with a peak integrated enhancement of up to 300 and a peak hotspot enhancement of 105. The supercrystal polaritons induce pairs of incoming and outgoing resonances in the enhanced cross section as we demonstrate experimentally by measuring surface-enhanced Raman scattering with multiple laser wavelengths across the polariton resonance. The infrared absorption of polystyrene is likewise enhanced inside the supercrystals with a maximum enhancement of 400%. We show with a coupled oscillator model that the increase originates from the combined effects of hotspot formation and the excitation of standing polariton waves. Our work clearly relates the structural and optical properties of plasmonic supercrystals and shows that such crystals are excellent hosts and substrates for the uniform and predictable enhancement of vibrational spectra.

Raman Scattering Cross Section of Confined Carbyne.

We experimentally quantify the Raman scattering from individual carbyne chains confined in double-walled carbon nanotubes. We find that the resonant differential Raman cross section of confined carbyne is on the order of 10-22 cm2 sr-1 per atom, making it the strongest Raman scatterer ever reported.

Few-Wall Carbon Nanotube Coils.

While various electronic components based on carbon nanotubes (CNTs) have already been demonstrated, the realization of miniature electromagnetic coils based on CNTs remains a challenge. Coils made of single-wall CNTs with accessible ends for contacting have been recently demonstrated but were found unsuitable to act as electromagnetic coils because of electrical shorting between their turns. Coils made of a few-wall CNT could in principle allow an insulated flow of current and thus be potential candidates for realizing CNT-based electromagnetic coils. However, no such CNT structure has been produced so far. Here, we demonstrate the formation of few-wall CNT coils and characterize their structural, optical, vibrational, and electrical properties using experimental and computational tools. The coils are made of CNTs with 2, 3, or 4 walls. They have accessible ends for electrical contacts and low defect densities. The coil diameters are on the order of one micron, like those of single-wall CNT coils, despite the higher rigidity of few-wall CNTs. Coils with as many as 163 turns were found, with their turns organized in a rippled raft configuration. These coils are promising candidates for a variety of miniature devices based on electromagnetic coils, such as electromagnets, inductors, transformers, and motors. Being chirally and enantiomerically pure few-wall CNT bundles, they are also ideal for fundamental studies of interwall coupling and superconductivity in CNTs.

Separation of Specific Single-Enantiomer Single-Wall Carbon Nanotubes in the Large-Diameter Regime.

The enantiomer-level isolation of single-walled carbon nanotubes (SWCNTs) in high concentration and with high purity for nanotubes greater than 1.1 nm in diameter is demonstrated using a two-stage aqueous two-phase extraction (ATPE) technique. In total, five different nanotube species of ∼1.41 nm diameter are isolated, including both metallics and semiconductors. We characterize these populations by absorbance spectroscopy, circular dichroism spectroscopy, resonance Raman spectroscopy, and photoluminescence mapping, revealing and substantiating mod-dependent optical dependencies. Using knowledge of the competitive adsorption of surfactants to the SWCNTs that controls partitioning within the ATPE separation, we describe an advanced acid addition methodology that enables the fine control of the separation of these select nanotubes. Furthermore, we show that endohedral filling is a previously unrecognized but important factor to ensure a homogeneous starting material and further enhance the separation yield, with the best results for alkane-filled SWCNTs, followed by empty SWCNTs, with the intrinsic inhomogeneity of water-filled SWCNTs causing them to be worse for separations. Lastly, we demonstrate the potential use of these nanotubes in field-effect transistors.

Separation of Small-Diameter Single-Walled Carbon Nanotubes in One to Three Steps with Aqueous Two-Phase Extraction.

An aqueous two-phase extraction (ATPE) technique capable of separating small-diameter single-walled carbon nanotubes in one, two, or at the most three steps is presented. Separation is performed in the well-studied two-phase system containing polyethylene glycol and dextran, but it is achieved without changing the global concentration or ratio of cosurfactants. Instead, the technique is reliant upon the different surfactant shell around each nanotube diameter at a fixed surfactant concentration. The methodology to obtain a single set of surfactant conditions is provided, and strategies to optimize these for other diameter regimes are discussed. In total, 11 different chiralities in the diameter range 0.69-0.91 nm are separated. These include semiconducting and both armchair and nonarmchair metallic nanotube species. Titration of cosurfactant suspensions reveal separation to be driven by the pH of the suspension with each ( n, m) species partitioning at a fixed pH. This allows for an ( n, m) separation approach to be presented that is as simple as pipetting known volumes of acid into the ATPE system.

Fluorescent Polymer-Single-Walled Carbon Nanotube Complexes with Charged and Noncharged Dendronized Perylene Bisimides for Bioimaging Studies.

Fluorescent nanomaterials are expected to revolutionize medical diagnostic, imaging, and therapeutic tools due to their superior optical and structural properties. Their inefficient water solubility, cell permeability, biodistribution, and high toxicity, however, limit the full potential of their application. To overcome these obstacles, a water-soluble, fluorescent, cytocompatible polymer-single-walled carbon nanotube (SWNT) complex is introduced for bioimaging applications. The supramolecular complex consists of an alkylated polymer conjugated with neutral hydroxylated or charged sulfated dendronized perylene bisimides (PBIs) and SWNTs as a general immobilization platform. The polymer backbone solubilizes the SWNTs, decorates them with fluorescent PBIs, and strongly improves their cytocompatibility by wrapping around the SWNT scaffold. In photophysical measurements and biological in vitro studies, sulfated complexes exhibit superior optical properties, cellular uptake, and intracellular staining over their hydroxylated analogs. A toxicity assay confirms the highly improved cytocompatibility of the polymer-wrapped SWNTs toward surfactant-solubilized SWNTs. In microscopy studies the complexes allow for the direct imaging of the SWNTs' cellular uptake via the PBI and SWNT emission using the 1st and 2nd optical window for bioimaging. These findings render the polymer-SWNT complexes with nanometer size, dual fluorescence, multiple charges, and high cytocompatibility as valuable systems for a broad range of fluorescence bioimaging studies.

Inner- and outer-wall sorting of double-walled carbon nanotubes.

Double-walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single-walled carbon nanotubes (SWCNTs), and previous sorting methods only achieved outer-wall electronic-type selectivity. Here, a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer-wall electronic type is presented. Electronic coupling between the inner and outer wall is used to alter the surfactant coating around each of the DWCNT types, and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO-BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high purity of the resulting fractions is verified by absorption measurements, transmission electron microscopy, atomic force microscopy, resonance Raman mapping and high-density field-effect transistor devices.

Preserving π-conjugation in covalently functionalized carbon nanotubes for optoelectronic applications.

Covalent functionalization tailors carbon nanotubes for a wide range of applications in varying environments. Its strength and stability of attachment come at the price of degrading the carbon nanotubes sp2 network and destroying the tubes electronic and optoelectronic features. Here we present a non-destructive, covalent, gram-scale functionalization of single-walled carbon nanotubes by a new [2+1] cycloaddition. The reaction rebuilds the extended π-network, thereby retaining the outstanding quantum optoelectronic properties of carbon nanotubes, including bright light emission at high degree of functionalization (1 group per 25 carbon atoms). The conjugation method described here opens the way for advanced tailoring nanotubes as demonstrated for light-triggered reversible doping through photochromic molecular switches and nanoplasmonic gold-nanotube hybrids with enhanced infrared light emission.