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.

Raman spectroscopy uses visible light to acquire vibrational fingerprints of molecules, thus making it a powerful tool for chemical analysis in a wide range of media. Its potential for optical imaging at high resolution is, however, severely limited by the fact that the Raman effect is weak. Here, we report the discovery of a giant Raman scattering effect from encapsulated and aggregated dye molecules inside single-walled carbon nanotubes (SWNTs). Measurements performed on rod-like dyes, such as α-sexithiophene and βcarotene, assembled inside SWNTs as highly polarizable J-aggregates indicate a resonant Raman cross-section (CS) of ~10-21 cm 2 /sr, which is well above the CS required for detecting individual aggregates at the highest optical resolution. Free from fluorescence background and photobleaching, this giant Raman effect allows the realization of a library of functionalized and biocompatible nanoprobe labels for Raman imaging with robust detection using multispectral analysis.

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 ΔH = (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.

The in cellulo assembly of plasmonic nanomaterials into photo-responsive probes is of great interest for many bioimaging and nanophotonic applications but remains challenging with traditional nucleic acid scaffolds-based bottom-up methods. Here, we address this quandary using split-fluorescent protein (FP) fragments as molecular glue and switchable Raman reporters to assemble gold or silver plasmonic nanoparticles (NPs) into photonic clusters directly in live cells. When targeted to diffusing surface biomarkers in cancer cells, the NPs self-assemble into surface-enhanced Raman-scattering (SERS) nanoclusters having hot spots homogenously seeded by the reconstruction of full-length FPs. Within plasmonic hot spots, autocatalytic activation of the FP chromophore and near-field amplification of its Raman fingerprints enable selective and sensitive SERS imaging of targeted cells. This FP-driven assembly of metal colloids also yields enhanced photoacoustic signals, allowing the hybrid FP/NP nanoclusters to serve as contrast agents for multimodal SERS and photoacoustic microscopy with single-cell sensitivity.

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 10 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 (10). 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.

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.

imaging is presented as a powerful method to acquire quantitative as well as qualitative information on lowdimensional materials. The method is, however, not widely used due to limitations of the Raman scanning instruments. Here we present a hyperspectral Raman system based on Bragg tunable filtering that is capable of global imaging with significantly reduced acquisition time and improved sensitivity compared to scanning confocal Raman microscopes. The operation principles of the instrument are presented, and the performance is benchmarked using a calibrated carbon nanotube sample. Examples of various applications are shown to illustrate the abilities of the technique to characterize samples deposited on oxidized silicon substrates, including graphene stacks prepared by chemical-vapor deposition, exfoliated MoS 2 , and carbon nanotubes filled with dye molecules. The wealth of information available through this hyperspectral Raman imaging technique opens many new ways to probe the properties of complex low-dimensional materials.

No abstract