Structurally well-defined graphene nanoribbons (GNRs) have emerged as highly promising materials for the next-generation nanoelectronics. The electronic properties of GNRs critically depend on their edge topologies. Here, we demonstrate the efficient synthesis of a curved GNR (cGNR) with a combined cove, zigzag, and armchair edge structure, through bottom-up synthesis. The curvature of the cGNR is elucidated by the corresponding model compounds tetrabenzo­[a,cd,j,lm]­perylene (1) and diphenanthrene-fused tetrabenzo­[a,cd,j,lm]­perylene (2), the structures of which are unambiguously confirmed by the X-ray single-crystal analysis. The resultant multi-edged cGNR exhibits a well-resolved absorption at the near-infrared (NIR) region with a maximum peak at 850 nm, corresponding to a narrow optical energy gap of ∼1.22 eV. Employing THz spectroscopy, we disclose a long scattering time of ∼60 fs, corresponding to a record intrinsic charge carrier mobility of ∼600 cm2 V–1 s–1 for photogenerated charge carriers in cGNR.

The block copolymer self-assembly approach has received great attention in recent years as a possible way to overcome the limits of conventional lithography and to fabricate sub-22 nm structures. At this level, precise nanometric control is crucial for technological applications and the search for a flexible and reproducible protocol is a great challenge. The polystyrene-b-poly(methylmethacrylate) (PS-b-PMMA) system, with a styrene fraction of 0.71, spontaneously separates into a periodic array of hexagonally packed PMMA cylinders embedded in a matrix of PS and, under suitable processing conditions, this is perpendicularly oriented with respect to the underlying substrate. The selective removal of the PMMA allows us to obtain a nanoporous PS matrix with well-defined pore dimensions. Perpendicular orientation of the PMMA cylinders requires surface neutralization by means of a suitable PS-r-PMMA random copolymer. The choice of the random copolymer is not trivial, because different PS-r-PMMA copolymers strongly affect the characteristics of the PS-b-PMMA film deposited on it. In this paper the effects of the selected PS-r-PMMA on the arrangement as well as on the peculiar dimensions (pore diameter, pore to pore distance) of the final nanoporous PS thin film are studied. Reliable protocols for the fabrication of a disposable polymeric mask are proposed in view of its application in advanced lithographic processes.

Vertically aligned GaN nanorod arrays with nonpolar InGaN/GaN multi quantum wells (MQW) were grown by MOVPE on c-plane GaN-on-sapphire templates. The chemical and structural properties of single nanorods are optically investigated with a spatial resolution beyond the diffraction limit using tip-enhanced Raman spectroscopy (TERS). This enables the local mapping of variations in the chemical composition, charge distribution, and strain in the MQW region of the nanorods. Nanoscale fluctuations of the In content in the InGaN layer of a few percent can be identified and visualized with a lateral resolution below 35 nm. We obtain evidence for the presence of indium clustering and the formation of cubic inclusions in the wurtzite matrix near the QW layers. These results are directly confirmed by high-resolution TEM images, revealing the presence of stacking faults and different polymorphs close to the surface near the MQW region. The combination of TERS and HRTEM demonstrates the potential of this nanoscale near-field imaging technique, establishing TERS as a very potent, comprehensive, and nondestructive tool for the characterization and optimization of technologically relevant semiconductor nanostructures.

We present an experimental study on the near-field light-matter interaction by tip-enhanced Raman scattering (TERS) with polarized light in three different materials: germanium-doped gallium nitride (GaN), graphene, and carbon nanotubes. We investigate the dependence of the TERS signal on the incoming light polarization and on the sample carrier concentration, as well as the Raman selection rules in the near-field. We explain the experimental data with a tentative quantum mechanical interpretation, which takes into account the role of plasmon polaritons, and the associated evanescent field. The driving force for the breakdown of the classical Raman selection rules in TERS is caused by photon tunneling through the perturbation of the evanescent field, with the consequent polariton annihilation. Predictions based on this quantum mechanical approach are in good agreement with the experimental data, which are shown to be independent of incoming light polarization, leading to new Raman selection rules for TERS.

The self-assembly of block-copolymer thin films in periodic nanostructures has received considerable attention during the last decade due to their potential applications in nanofabrication and nanolithography. We followed the morphologies developed in thin films of a cylinder-forming diblock copolymer polystyrene-b-poly(methylmethacrylate) ((PS-b-PMMA), PS 46.1 kg mol( - 1), PMMA 21.0 kg mol( - 1), lattice spacing L(0) = 36 nm), as a function of the film thickness (t), analyzing the effect of thickness commensurability on domain orientation in respect to the substrate. The study was circumscribed to the unexplored range of thickness below L(0). Two thickness windows with perpendicular orientation of the PMMA domains were identified: a well-known window at t approximately L(0) and a new window at t approximately L(0)/2. A half-parallel cylinder morphology was observed for [Formula: see text] with a progressive change in morphology [Formula: see text] when thickness increases from L(0)/2 to L(0). This experimental evidence provides new insights on the mechanism of block copolymers self-organization and indicates the possibility to tune the thickness of the nanostructured polymeric film below L(0), allowing the fabrication of ultrathin soft masks for advanced lithographic processes.