Diameter-dependent single- and double-file stacking of squaraine dye molecules inside chirality-sorted single-wall carbon nanotubes.

The filling of single-wall carbon nanotubes (SWCNTs) with dye molecules has become a novel path to add new functionalities through the mutual interaction of confined dyes and host SWCNTs. In particular cases, the encapsulated dye molecules form strongly interacting molecular arrays and these result in severely altered optical properties of the dye molecules. Here, we present the encapsulation of a squaraine dye inside semiconducting chirality-sorted SWCNTs with diameters ranging from ∼1.15 nm, in which the dye molecules can only be encapsulated in a single-file molecular arrangement, up to ∼1.5 nm, in which two or three molecular files can fit side-by-side. Through the chirality-selective observation of energy transfer from the dye molecules to the surrounding SWCNTs, we find that the absorption wavelength of the dye follows a peculiar SWCNT diameter dependence, originating from the specific stacking of the dye inside the host SWCNTs. Corroborated by a theoretical model, we find that for each SWCNT diameter, the dye molecules adopt a close packing geometry, resulting in tunable optical properties of the hybrid when selecting a specific SWCNT chirality.

Efficient Inner-to-Outer Wall Energy Transfer in Highly Pure Double-Wall Carbon Nanotubes Revealed by Detailed Spectroscopy.

The coaxial stacking of two single-wall carbon nanotubes (SWCNTs) into a double-wall carbon nanotube (DWCNT), forming a so-called one-dimensional van der Waals structure, leads to synergetic effects that dramatically affect the optical and electronic properties of both layers. In this work, we explore these effects in purified DWCNT samples by combining absorption, wavelength-dependent infrared fluorescence-excitation (PLE), and wavelength-dependent resonant Raman scattering (RRS) spectroscopy. Purified DWCNTs are obtained by careful solubilization that strictly avoids ultrasonication or by electronic-type sorting, both followed by a density gradient ultracentrifugation to remove unwanted SWCNTs that could obscure the DWCNT characterization. Chirality-dependent shifts of the radial breathing mode vibrational frequencies and transition energies of the inner and outer DWCNT walls with respect to their SWCNT analogues are determined by advanced two-dimensional fitting of RRS and PLE data of DWCNT and their reference SWCNT samples. This exhaustive data set verifies that fluorescence from the inner DWCNT walls of well-purified samples is severely quenched through efficient energy transfer from the inner to the outer DWCNT walls. Combined analysis of the PLE and RRS results further reveals that this transfer is dependent on the inner and outer wall chirality, and we identify the specific combinations dominant in our DWCNT samples. These obtained results demonstrate the necessity and value of a combined structural characterization approach including PLE and RRS spectroscopy for bulk DWCNT samples.

Simple and rapid gas sensing using a single-walled carbon nanotube field-effect transistor-based logic inverter.

Single-walled carbon nanotubes (SWCNTs) are promising candidates for gas sensing applications, providing an efficient solution to the device miniaturization challenge and allowing low power consumption. SWCNT gas sensors are mainly based on field-effect transistors (SWCNT-FETs) where the modification of the current flowing through the nanotube is used for gas detection. A major limitation of these SWCNT-FETs lies in the difficulty to measure their transfer curves, since the flowing current typically varies between 10-12 and 10-3 A. Thus, voluminous and energy consuming systems are necessary, severely limiting the miniaturization and low energy consumption. Here, we propose an inverter device that combines two SWCNT-FETs which brings a concrete solution to these limitations and simplifies data processing. In this innovative sensing configuration, the gas detection is based on the variation of an electric potential in the volt range instead of a current intensity variation in the microampere range. In this study, the proof of concept is performed using NO2 gas but can be easily extended to a wide range of gases.

Tuning bimetallic catalysts for a selective growth of SWCNTs.

Recent advances in structural control during the synthesis of SWCNTs have in common the use of bimetallic nanoparticles as catalysts, despite the fact that their exact role is not fully understood. We therefore analyze the effect of the catalyst's chemical composition on the structure of the resulting SWCNTs by comparing three bimetallic catalysts (FeRu, CoRu and NiRu). A specific synthesis protocol is designed to impede the catalyst nanoparticle coalescence mechanisms and stabilize their diameter distributions throughout the growth. Owing to the ruthenium component which has a limited carbon solubility, tubes grow in tangential mode and their diameter is close to that of their seeding nanoparticles. By using the as-synthesized SWCNTs as a channel material infield effect transistors, we show how the chemical composition of the catalysts and temperature can be used as parameters to tune the diameter distribution and semiconducting-to-metallic ratio of SWCNT samples. Finally, a phenomenological model, based on the dependence of the carbon solubility as a function of catalyst nanoparticle size and nature of the alloying elements, is proposed to interpret the results.