Advanced 1D heterostructures based on nanotube templates and molecules.

Recent advancements in materials science have shed light on the potential of exploring hierarchical assemblies of molecules on surfaces, driven by both fundamental and applicative challenges. This field encompasses diverse areas including molecular storage, drug delivery, catalysis, and nanoscale chemical reactions. In this context, the utilization of nanotube templates (NTs) has emerged as promising platforms for achieving advanced one-dimensional (1D) molecular assemblies. NTs offer cylindrical, crystalline structures with high aspect ratios, capable of hosting molecules both externally and internally (Mol@NT). Furthermore, NTs possess a wide array of available diameters, providing tunability for tailored assembly. This review underscores recent breakthroughs in the field of Mol@NT. The first part focuses on the diverse panorama of structural properties in Mol@NT synthesized in the last decade. The advances in understanding encapsulation, adsorption, and ordering mechanisms are detailed. In a second part, the review highlights the physical interactions and photophysics properties of Mol@NT obtained by the confinement of molecules and nanotubes in the van der Waals distance regime. The last part of the review describes potential applicative fields of these 1D heterostructures, providing specific examples in photovoltaics, luminescent materials, and bio-imaging. A conclusion gathers current challenges and perspectives of the field to foster discussion in related communities.

Momentum-Resolved Dielectric Response of Free-Standing Mono-, Bi-, and Trilayer Black Phosphorus.

Black phosphorus (BP), a 2D semiconducting material of interest in electronics and photonics, exhibits physical properties characterized by strong anisotropy and band gap energy that scales with reducing layer number. However, the investigation of its intrinsic properties is challenging because thin-layer BP is photo-oxidized under ambient conditions and the energy of its electronic states shifts in different dielectric environments. We prepared free-standing samples of few-layer BP under glovebox conditions and probed the dielectric response in a vacuum using scanning transmission electron microscopy and electron energy loss spectroscopy (STEM-EELS). Thresholds of the excitation energy are measured at 1.9, 1.4, and 1.1 eV for the mono-, bi-, and trilayer BP, respectively, and these values are used to estimate the corresponding optical band gaps. A comparison of our results with electronic structure calculations indicates that the variation of the quasi-particle gap is larger than that of the exciton binding energy. The dispersion of the plasmons versus momentum for one- to three-layer BP and bulk BP highlights a deviation from parabolic to linear dispersion and strong anisotropic fingerprints.

Plasmonic enhancement of SERS measured on molecules in carbon nanotubes.

We isolated the plasmonic contribution to surface-enhanced Raman scattering (SERS) and found it to be much stronger than expected. Organic dyes encapsulated in single-walled carbon nanotubes are ideal probes for quantifying plasmonic enhancement in a Raman experiment. The molecules are chemically protected through the nanotube wall and spatially isolated from the metal, which prevents enhancement by chemical means and through surface roughness. The tubes carry molecules into SERS hotspots, thereby defining molecular position and making it accessible for structural characterization with atomic-force and electron microscopy. We measured a SERS enhancement factor of 106 on α-sexithiophene (6T) molecules in the gap of a plasmonic nanodimer. This is two orders of magnitude stronger than predicted by the electromagnetic enhancement theory (104). We discuss various phenomena that may explain the discrepancy (including hybridization, static and dynamic charge transfer, surface roughness, uncertainties in molecular position and orientation), but found all of them lacking in enhancement for our probe system. We suggest that plasmonic enhancement in SERS is, in fact, much stronger than currently anticipated. We discuss novel approaches for treating SERS quantum mechanically that appear promising for predicting correct enhancement factors. Our findings have important consequences on the understanding of SERS as well as for designing and optimizing plasmonic substrates.

Photooxidation and quantum confinement effects in exfoliated black phosphorus.

Thin layers of black phosphorus have recently raised interest owing to their two-dimensional (2D) semiconducting properties, such as tunable direct bandgap and high carrier mobilities. This lamellar crystal of phosphorus atoms can be exfoliated down to monolayer 2D-phosphane (also called phosphorene) using procedures similar to those used for graphene. Probing the properties has, however, been challenged by a fast degradation of the thinnest layers on exposure to ambient conditions. Herein, we investigate this chemistry using in situ Raman and transmission electron spectroscopies. The results highlight a thickness-dependent photoassisted oxidation reaction with oxygen dissolved in adsorbed water. The oxidation kinetics is consistent with a phenomenological model involving electron transfer and quantum confinement as key parameters. A procedure carried out in a glove box is used to prepare mono-, bi- and multilayer 2D-phosphane in their pristine states for further studies on the effect of layer thickness on the Raman modes. Controlled experiments in ambient conditions are shown to lower the A(g)(1)/A(g)(2) intensity ratio for ultrathin layers, a signature of oxidation.

Fano resonances in the midinfrared spectra of single-walled carbon nanotubes.

This work revisits the physics giving rise to the carbon nanotube phonon bands in the midinfrared. Our measurements of doped and undoped samples of single-walled carbon nanotubes in Fourier transform infrared spectroscopy show that the phonon bands exhibit an asymmetric line shape and that their effective cross section is enhanced upon doping. We relate these observations to electron-phonon coupling or, more specifically, to a Fano resonance phenomenon. We note that the dopant-induced intraband (not interband) continuum couples strongly to the phonon modes, and that defects created on the sidewall are scattering centers that increase the spectral amplitude of the resonance.

Optical microcavity with semiconducting single-wall carbon nanotubes.

We report studies of optical Fabry-Perot microcavities based on semiconducting single-wall carbon nanotubes with a quality factor of 160. We experimentally demonstrate a huge photoluminescence signal enhancement by a factor of 30 in comparison with the identical film and by a factor of 180 if compared with a thin film containing non-purified (8,7) nanotubes. Furthermore, the spectral full-width at half-maximum of the photo-induced emission is reduced down to 8 nm with very good directivity at a wavelength of about 1.3 microm. Such results prove the great potential of carbon nanotubes for photonic applications.

Confinement of Dyes inside Boron Nitride Nanotubes: Photostable and Shifted Fluorescence down to the Near Infrared.

Fluorescence is ubiquitous in life science and used in many fields of research ranging from ecology to medicine. Among the most common fluorogenic compounds, dyes are being exploited in bioimaging for their outstanding optical properties from UV down to the near IR (NIR). However, dye molecules are often toxic to living organisms and photodegradable, which limits the time window for in vivo experiments. Here, it is demonstrated that organic dye molecules are passivated and photostable when they are encapsulated inside a boron nitride nanotube (dyes@BNNT). The results show that the BNNTs drive an aggregation of the encapsulated dyes, which induces a redshifted fluorescence from visible to NIR-II. The fluorescence remains strong and stable, exempt of bleaching and blinking, over a time scale longer than that of free dyes by more than 104 . This passivation also reduces the toxicity of the dyes and induces exceptional chemical robustness, even in harsh conditions. These properties are highlighted in bioimaging where the dyes@BNNT nanohybrids are used as fluorescent nanoprobes for in vivo monitoring of Daphnia Pulex microorganisms and for diffusion tracking on human hepatoblastoma cells with two-photon imaging.

Resonant, Plasmonic Raman Enhancement of α-6T Molecules Encapsulated in Carbon Nanotubes.

Surface-enhanced Raman scattering (SERS) and resonant Raman scattering are widely used techniques to enhance the Raman intensity of molecules and nanomaterials by several orders of magnitude. In SERS, typically, molecules are investigated and their intrinsic resonance is often ignored while discussing the plasmonic enhancement. Here, we study α-sexithiophenes encapsulated in carbon nanotubes placed in the center of a nanodimer. By dielectrophoretic deposition, we place the nanotubes precisely in the center of a plasmonic gold nanodimer and observe SERS enhancement from individual tube bundles. The encapsulated molecules are not subjected to chemical enhancement because of the protective character of the nanotube. Polarization-dependent Raman measurements confirm the alignment of the molecules within the carbon nanotubes (CNTs) and reveal the influence of the plasmonic near field on the molecule's Raman intensity. We investigate the encapsulated molecules in small CNT bundles with and without plasmonic enhancement and determine the molecular and plasmonic resonance by tuning the excitation wavelength. We observe a strong red shift of the maximum Raman intensity under plasmonic enhancement toward the plasmon resonance.

Aggregation Control of α-Sexithiophene via Isothermal Encapsulation Inside Single-Walled Carbon Nanotubes.

Liquid-phase encapsulation of α-sexithiophene (6T) molecules inside individualized single-walled carbon nanotubes (SWCNTs) is investigated using Raman imaging and spectroscopy. By taking advantage of the strong Raman response of this system, we probe the encapsulation isotherms at 30 and 115 °C using a statistical ensemble of SWCNTs deposited on a oxidized silicon substrate. Two distinct and sequential stages of encapsulation are observed: Stage 1 is a one-dimensional (1D) aggregation of 6T aligned head-to-tail inside the nanotube, and stage 2 proceeds with the assembly of a second row, giving pairs of aligned 6Ts stacked together side-by-side. The experimental data are fitted using both Langmuir (type VI) and Ising models, in which the single-aggregate (stage 1) forms spontaneously, whereas the pair-aggregate (stage 2) is endothermic in toluene with formation enthalpy of ΔHpair = (260 ± 20) meV. Tunable Raman spectroscopy for each stage reveals a bathochromic shift of the molecular resonance of the pair-aggregate, which is consistent with strong intermolecular coupling and suggestive of J-type aggregation. This quantitative Raman approach is sensitive to roughly 10 molecules per nanotube and provides direct evidence of molecular entry from the nanotube ends. These insights into the encapsulation process guide the preparation of well-defined 1D molecular crystals having tailored optical properties.

Light emission in silicon from carbon nanotubes.

The use of optics in microelectronic circuits to overcome the limitation of metallic interconnects is more and more considered as a viable solution. Among future silicon compatible materials, carbon nanotubes are promising candidates thanks to their ability to emit, modulate, and detect light in the wavelength range of silicon transparency. We report the first integration of carbon nanotubes with silicon waveguides, successfully coupling their emission and absorption properties. A complete study of this coupling between carbon nanotubes and silicon waveguides was carried out, which led to the demonstration of the temperature-independent emission from carbon nanotubes in silicon at a wavelength of 1.3 µm. This represents the first milestone in the development of photonics based on carbon nanotubes on silicon.