In Operando Study of Charge Modulation in MoS2 Transistors by Excitonic Reflection Microscopy.

Monolayers of transition metal dichalcogenides (2D TMDs) experience strong modulation of their optical properties when the charge density is varied. Indeed, the transition from carriers composed mostly of excitons at low electron density to a situation in which trions dominate at high density is accompanied by a significant evolution of both the refractive index and the extinction coefficient. Using optical interference reflection microscopy at the excitonic wavelength, this (n, κ)-q relationship can be exploited to directly image the electron density in operating TMD devices. In this work, we show how this technique, which we call XRM (excitonic reflection microscopy), can be used to study charge distribution in MoS2 field-effect transistors with subsecond throughput, in wide-field mode. Complete maps of the charge distribution in the transistor channel at any drain and gate bias polarization point (VDS, VGS) are obtained, at ∼3 orders of magnitude faster than with scanning probe techniques such as KPFM. We notably show how the advantages of XRM enable real-time mapping of bias-dependent charge inhomogeneities, the study of resistive delays in 2D polycrystalline networks, and the evaluation of the VDS vs VGS competition to control the charge distribution in active devices.

Tailoring carbon nanotubes optical properties through chirality-wise silicon ring resonators.

Semiconducting single walled carbon nanotubes (s-SWNT) have an immense potential for the development of active optoelectronic functionalities in ultra-compact hybrid photonic circuits. Specifically, s-SWNT have been identified as a very promising solution to implement light sources in the silicon photonics platform. Still, two major challenges remain to fully exploit the potential of this hybrid technology: the limited interaction between s-SWNTs and Si waveguides and the low quantum efficiency of s-SWNTs emission. Silicon micro-ring resonators have the potential capability to overcome these limitations, by providing enhanced light s-SWNT interaction through resonant light recirculation. Here, we demonstrate that Si ring resonators provide SWNT chirality-wise photoluminescence resonance enhancement, releasing a new degree of freedom to tailor s-SWNT optical properties. Specifically, we show that judicious design of the micro-ring geometry allows selectively promoting the emission enhancement of either (8,6) or (8,7) SWNT chiralities present in a high-purity polymer-sorted s-SWNT solution. In addition, we present an analysis of nanometric-sized silicon-on-insulator waveguides that predicts stronger light s-SWNT interaction for transverse-magnetic (TM) modes than for conventionally used transverse-electric (TE) modes.

Narrow-linewidth carbon nanotube emission in silicon hollow-core photonic crystal cavity.

Polymer-sorted semiconducting single-walled carbon nanotubes (SWNTs) provide room-temperature emission at near-infrared wavelengths, with potential for large volume production of high-quality solutions and wafer-scale deposition. These features make SWNTs a very attractive material for the realization of on-chip light sources. Coupling SWNT into optical microcavities could enhance and guide their emission, while enabling spectral selection by cavity resonance engineering. This could allow the realization of bright, narrowband sources. Here, we report the first demonstration of coupling SWNTs into the resonant modes of Si hollow-core photonic crystal cavities. We exploit the strong evanescent field in these resonators to interact with SWNT emission, coupling it into an integrated access waveguide. Based on this concept, we demonstrate narrowband SWNT emission resonantly coupled into a Si bus waveguide with a full width at half-maximum of 0.34 nm and an off-resonance rejection exceeding 5 dB.

Polymer-Decorated Carbon Nanotubes as Transducers for Label-Free Photonic Biosensors.

A biosensor taking advantage of the optical properties of sorted carbon nanotubes has been developed. A polyfluorene polymer bearing azido groups was synthesized and used for the selective extraction of semi-conducting nanotubes from the bulk population. The resulting polymer-decorated nanotubes were then conjugated by click-chemistry to a ligand unit (biotin), and the sensing properties of the biotinylated nanotubes were investigated by photoluminescence measurements, upon interaction with the streptavidin target.

Diameter-Selective Dispersion of Carbon Nanotubes via Polymers: A Competition between Adsorption and Bundling.

The mechanism of the selective dispersion of single-walled carbon nanotubes (CNTs) by polyfluorene polymers is studied in this paper. Using extensive molecular dynamics simulations, it is demonstrated that diameter selectivity is the result of a competition between bundling of CNTs and adsorption of polymers on CNT surfaces. The preference for certain diameters corresponds to local minima of the binding energy difference between these two processes. Such minima in the diameter dependence occur due to abrupt changes in the CNT's coverage with polymers, and their calculated positions are in quantitative agreement with preferred diameters reported experimentally. The presented approach defines a theoretical framework for the further understanding and improvement of dispersion/extraction processes.

Single-step preparation of TiO2/MWCNT Nanohybrid materials by laser pyrolysis and application to efficient photovoltaic energy conversion.

This paper presents the continuous-flowand single-step synthesis of a TiO2/MWCNT (multiwall carbon nanotubes) nanohybrid material. The synthesis method allows achieving high coverage and intimate interface between the TiO2particles and MWCNTs, together with a highly homogeneous distribution of nanotubes within the oxide. Such materials used as active layer in theporous photoelectrode of solid-state dye-sensitized solar cells leads to a substantial performance improvement (20%) as compared to reference devices.

Carbon nanotube-templated synthesis of covalent porphyrin network for oxygen reduction reaction.

The development of innovative techniques for the functionalization of carbon nanotubes that preserve their exceptional quality, while robustly enriching their properties, is a central issue for their integration in applications. In this work, we describe the formation of a covalent network of porphyrins around MWNT surfaces. The approach is based on the adsorption of cobalt(II) meso-tetraethynylporphyrins on the nanotube sidewalls followed by the dimerization of the triple bonds via Hay-coupling; during the reaction, the nanotube acts as a template for the formation of the polymeric layer. The material shows an increased stability resulting from the cooperative effect of the multiple π-stacking interactions between the porphyrins and the nanotube and by the covalent links between the porphyrins. The nanotube hybrids were fully characterized and tested as the supported catalyst for the oxygen reduction reaction (ORR) in a series of electrochemical measurements under acidic conditions. Compared to similar systems in which monomeric porphyrins are simply physisorbed, MWNT-CoP hybrids showed a higher ORR activity associated with a number of exchanged electrons close to four, corresponding to the complete reduction of oxygen into water.

Synthesis of a multibranched porphyrin-oligonucleotide scaffold for the construction of DNA-based nano-architectures.

The interest in the functionalization of oligonucleotides with organic molecules has grown considerably over the last decade. In this work, we report on the synthesis and characterization of porphyrin-oligonucleotide hybrids containing one to four DNA strands (P1-P4). The hybrid P4, which inserts one porphyrin and four DNA fragments, was combined with gold nanoparticles and imaged by transmission electron microscopy.

Supramolecular chemistry of carbon nanotubes.

This chapter aims to present recent examples of supramolecular functionalization of carbon nanotubes. The non-covalent functionalization appears as a solution for the future applications in nanotechnologies since it allows the functionalization and manipulation of nanotubes without the introduction of sp (3) defects in the π-conjugated system. Thus, the optical and electronic properties of the nanotubes remain preserved. In the first part of this chapter, we present the use of surfactant for the dispersion of nanotubes and its application for sorting. Then we report several examples of functionalization of nanotubes based on π-stacking interactions with pyrene derivatives. Finally, in the last part we review the wrapping of photo/electroactive polymers around the nanotube sidewalls. We put a particular focus on polyflurorene-based polymers and we show their utilization for the separation of nanotubes in diameter and chirality.

Neuromorphic function learning with carbon nanotube based synapses.

The principle of using nanoscale memory devices as artificial synapses in neuromorphic circuits is recognized as a promising way to build ground-breaking circuit architectures tolerant to defects and variability. Yet, actual experimental demonstrations of the neural network type of circuits based on non-conventional/non-CMOS memory devices and displaying function learning capabilities remain very scarce. We show here that carbon-nanotube-based memory elements can be used as artificial synapses, combined with conventional neurons and trained to perform functions through the application of a supervised learning algorithm. The same ensemble of eight devices can notably be trained multiple times to code successively any three-input linearly separable Boolean logic function despite device-to-device variability. This work thus represents one of the very few demonstrations of actual function learning with synapses based on nanoscale building blocks. The potential of such an approach for the parallel learning of multiple and more complex functions is also evaluated.

Selective adsorption of proteins on single-wall carbon nanotubes by using a protective surfactant.

The dispersion of highly hydrophobic carbon materials such as carbon nanotubes in biological media is a challenging issue. Indeed, the nonspecific adsorption of proteins occurs readily when the nanotubes are introduced in biological media; therefore, a methodology to control adsorption is in high demand. To address this issue, we developed a bifunctional linker derived from pyrene that selectively enables or prevents the adsorption of proteins on single-wall carbon nanotubes (SWNTs). We demonstrated that it is possible to decrease or completely suppress the adsorption of proteins on the nanotube sidewall by using proper functionalization (either covalent or noncovalent). By subsequently activating the functional groups on the nanotube derivatives, protein adsorption can be recovered and, therefore, controlled. Our approach is simple, straightforward, and potentially suitable for other biomolecules that contain thio or amino groups available for coupling.

DNA-templated Pd conductive metallic nanowires.

We here present a protocol for the metallization of DNA scaffolds by palladium. The method is based on the initial slow precipitation of palladium oxide onto DNA strands. A reduction step follows to create conductive metallic nanowires. The slow oxide precipitation approach enables the formation of thin and continuous coatings on the DNA strands with negligible parasitic metallization of the remaining substrate surface.

Recent advances in molecular electronics based on carbon nanotubes.

Carbon nanotubes (CNTs) have exceptional physical properties that make them one of the most promising building blocks for future nanotechnologies. They may in particular play an important role in the development of innovative electronic devices in the fields of flexible electronics, ultra-high sensitivity sensors, high frequency electronics, opto-electronics, energy sources and nano-electromechanical systems (NEMS). Proofs of concept of several high performance devices already exist, usually at the single device level, but there remain many serious scientific issues to be solved before the viability of such routes can be evaluated. In particular, the main concern regards the controlled synthesis and positioning of nanotubes. In our opinion, truly innovative use of these nano-objects will come from: (i) the combination of some of their complementary physical properties, such as combining their electrical and mechanical properties, (ii) the combination of their properties with additional benefits coming from other molecules grafted on the nanotubes, and (iii) the use of chemically- or bio-directed self-assembly processes to allow the efficient combination of several devices into functional arrays or circuits. In this article, we outline the main issues concerning the development of carbon nanotubes based electronics applications and review our recent results in the field.

Versatile functionalization of nanoelectrodes by oligonucleotides via pyrrole electrochemistry.

Surface modification at the nanometer scale is a challenge for the future of molecular electronics. In particular, the precise anchoring and electrical addressing of biological scaffolds such as complex DNA nanonetworks is of importance for generating bio-directed assemblies of nano-objects for nanocircuit purposes. Herein, we consider the individual modification of nanoelectrodes with different oligonucleotide sequences by an electrochemically driven co-polymerization process of pyrrole and modified oligonucleotide sequences bearing pyrrole monomers. We demonstrate that this one-step technique presents the advantages of simplicity, localization of surface modification, mechanical, biological and chemical stability of the coatings, and high lateral resolution.

Zn-porphyrin/Zn-phthalocyanine dendron for SWNT functionalisation.

SWNT-porphyrin/phthalocyanine conjugates are described and fully characterised; their optical and electrochemical properties are investigated.

Hierarchical functionalisation of single-wall carbon nanotubes with DNA through positively charged pyrene.

A simple and efficient method to link reversibly DNA to SWNTs via electrostatic interaction is reported. The DNA/nanotube hybrids are characterised by a combination of gel electrophoresis and AFM.

Assembly of a magnetic polyoxometalate on SWNTs.

Recently, the organisation of magnetic molecules on carbon nanotubes has raised much interest due to their possible interesting contribution to molecular spintronics. In this paper, we describe the assembly on SWNTs of a magnetic polyoxometalate encompassing a single cobalt ion (CoPOM) and its isostructural diamagnetic zinc analogue (ZnPOM). The simple magnetic behaviour of CoPOM and the availability of its diamagnetic counterpart render these POM@NTs systems interesting model compounds for the study of molecular electronics devices based on carbon nanotubes and magnetic molecules. The success and rate of the grafting have been investigated by electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, Raman scattering and magnetisation measurements. These characterisations altogether demonstrate the preservation of the structural and magnetic properties of the molecules upon functionalisation and the existence of an electronic communication between the molecules and the nanotubes.