No abstract

Plasmonics using metal nanoparticles (MNPs) has emerged as an important research subject in the field of photonics, electronics, and nanotechnology. Despite spectacular progress in recent years, accurate tuning and modeling of plasmon resonances over a wide spectral range using state-of-the-art fabrication methods are still challenging tasks. Here, we report on the fine-tuning of the localized surface plasmon resonance (LSPR) of metal nanoparticles over a wide spectral range from near-infrared to blue using nanosphere lithography (NSL). In this systematic study, we use NSL to fabricate triangular shaped metal nanostructures using gold, silver, copper, and aluminum. All structures were annealed up to 500 °C under a nitrogen atmosphere in order to study the effect of annealing on the LSPR. Structural changes were investigated using scanning electron microscopy and atomic force microscopy. UV-VIS spectroscopy was used to determine the LSPR spectral position for these structures. The LSPR peak position is ordered as copper, gold, silver, and aluminum (from low to high photon energy—ranging from near-infrared to blue). The rate at which the LSPR changes with respect to the increasing annealing temperature is determined to be (2.3 ± 0.3) nm/°C and (1.3 ± 0.1) nm/°C for Ag and Au, respectively, while Cu MNPs show a two-step relation with a steeper slope of (1.4 ± 0.3) nm/°C initially up to 275 °C followed by a shallower slope of (0.5 ± 0.1) nm/°C. The full width at half maximum of the LSPR increases from gold over silver and copper to aluminum. We also performed finite element method simulations to validate the experimental findings. Our results can have a significant impact in plasmonic applications where fine-tuning and accurate designing of the LSPR are important.

Tip-enhanced Raman spectroscopy (TERS) has experienced tremendous progress over the last two decades. Despite detecting single molecules and achieving sub-nanometer spatial resolution, attaining high TERS sensitivity is still a challenging task due to low reproducibility of tip fabrication, especially regarding very sharp tip apices. Here, we present an approach for achieving strong TERS sensitivity via a systematic study of the near-field enhancement properties in the so-called gap-mode TERS configurations using the combination of finite element method (FEM) simulations and TERS experiments. In the simulation study, a gold tip apex is fixed at 80 nm of diameter, and the substrate consists of 20 nm high gold nanodiscs with diameter varying from 5 nm to 120 nm placed on a flat extended gold substrate. The local electric field distributions are computed in the spectral range from 500 nm to 800 nm with the tip placed both at the center and the edge of the gold nanostructure. The model is then compared with the typical gap-mode TERS configuration, in which a tip of varying diameter from 2 nm to 160 nm is placed in the proximity of a gold thin film. Our simulations show that the tip-nanodisc combined system provides much improved TERS sensitivity compared to the conventional gap-mode TERS configuration. We find that for the same tip diameter, the spatial resolution achieved in the tip-nanodisc model is much better than that observed in the conventional gap-mode TERS, which requires a very sharp metal tip to achieve the same spatial resolution on an extended metal substrate. Finally, TERS experiments are conducted on gold nanodisc arrays using home-built gold tips to validate our simulation results. Our simulations provide a guide for designing and realization of both high-spatial resolution and strong TERS intensity in future TERS experiments.

We report the observation of a third crystalline polymorph, “form III”, of the well-studied electron-transporting conjugated polymer P(NDI2OD-T2) that exhibits end-on texture. This third polymorph of P(NDI2OD-T2) is distinguished from other polymorphs by having two monomer units incorporated along the backbone-stacking direction, resulting in a doubling of the c axis of the unit cell. Form III crystallites are realized by melt-annealing a thin film followed by slow cooling. The distinct packing of this third polymorph is established through the application of grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements combined with peak simulation of candidate unit cells. The discovery of a third polymorph of P(NDI2OD-T2) provides a fresh opportunity for studying structure/function relationships of this important semiconducting polymer.

Despite the great promise of InSe for electronic and optoelectronic applications, Fröhlich interaction plays an important role in electrical transport due to the polar nature of it, which can become more significant in reduced dimensionality. Here, we report on how the dimensionality influences the strength and nature of the Fröhlich polaronic effect in InSe with the aid of plasmonic hot electrons injection. Polar optical phonons couple to hot electrons via the Fröhlich interaction in InSe and enable us to monitor them in conventional Raman measurements. We observed that the intensity of these phonon modes initially increases gradually with decreasing layer number and then drops drastically from 7 L to 6 L (transition from quasi-direct to indirect bandgap at room temperature). Additionally, a gradual decrease of intensity of the polar modes with further decreasing layer number is observed due to the increasing indirect bandgap nature of InSe suggesting reduced Fröhlich coupling below this thickness.