Alternative nano-lithographic tools for shell-isolated nanoparticle enhanced Raman spectroscopy substrates.

Chemically synthesized metal nanoparticles (MNPs) have been widely used as surface-enhanced Raman spectroscopy (SERS) substrates for monitoring catalytic reactions. In some applications, however, the SERS MNPs, besides being plasmonically active, can also be catalytically active and result in Raman signals from undesired side products. The MNPs are typically insulated with a thin (∼3 nm), in principle pin-hole-free shell to prevent this. This approach, which is known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), offers many advantages, such as better thermal and chemical stability of the plasmonic nanoparticle. However, having both a high enhancement factor and ensuring that the shell is pin-hole-free is challenging because there is a trade-off between the two when considering the shell thickness. So far in the literature, shell insulation has been successfully applied only to chemically synthesized MNPs. In this work, we alternatively study different combinations of chemical synthesis (bottom-up) and lithographic (top-down) routes to obtain shell-isolated plasmonic nanostructures that offer chemical sensing capabilities. The three approaches we study in this work include (1) chemically synthesized MNPs + chemical shell, (2) lithographic substrate + chemical shell, and (3) lithographic substrate + atomic layer deposition (ALD) shell. We find that ALD allows us to fabricate controllable and reproducible pin-hole-free shells. We showcase the ability to fabricate lithographic SHINER substrates which report an enhancement factor of 7.5 × 103 ± 17% for our gold nanodot substrates coated with a 2.8 nm aluminium oxide shell. Lastly, by introducing a gold etchant solution to our fabricated SHINER substrate, we verified that the shells fabricated with ALD are truly pin-hole-free.

Ligand-controlled and nanoconfinement-boosted luminescence employing Pt(ii) and Pd(ii) complexes: from color-tunable aggregation-enhanced dual emitters towards self-referenced oxygen reporters.

In this work, we describe the synthesis, structural and photophysical characterization of four novel Pd(ii) and Pt(ii) complexes bearing tetradentate luminophoric ligands with high photoluminescence quantum yields (Φ L) and long excited state lifetimes (τ) at room temperature, where the results were interpreted by means of DFT calculations. Incorporation of fluorine atoms into the tetradentate ligand favors aggregation and thereby, a shortened average distance between the metal centers, which provides accessibility to metal-metal-to-ligand charge-transfer (3MMLCT) excimers acting as red-shifted energy traps if compared with the monomeric entities. This supramolecular approach provides an elegant way to enable room-temperature phosphorescence from Pd(ii) complexes, which are otherwise quenched by a thermal population of dissociative states due to a lower ligand field splitting. Encapsulation of these complexes in 100 nm-sized aminated polystyrene nanoparticles enables concentration-controlled aggregation-enhanced dual emission. This phenomenon facilitates the tunability of the absorption and emission colors while providing a rigidified environment supporting an enhanced Φ L up to about 80% and extended τ exceeding 100 µs. Additionally, these nanoarrays constitute rare examples for self-referenced oxygen reporters, since the phosphorescence of the aggregates is insensitive to external influences, whereas the monomeric species drop in luminescence lifetime and intensity with increasing triplet molecular dioxygen concentrations (diffusion-controlled quenching).

Positioning growth of NPB crystalline nanowires on the PTCDA nanocrystal template.

Non-planar organic molecules often form amorphous films via vapor phase deposition on surfaces. In this study, we demonstrate for the first time that direct crystalline growth of non-planar NPB is possible when the orientation of initially deposited molecules on a PTCDA nanocrystal template is controlled to make it analogous to the structure of the molecular crystal. The crystalline NPB nanowires can be further positioned by controlling the site-selective growth of PTCDA nanocrystal templates at pre-determined locations. Short channel bottom contact OFET array with the NPB nanowires directly grown on electrodes were subsequently fabricated. The hole mobility of NPB nanowires is improved by 40-fold in comparison to that of the amorphous films.

Controllable growth and field-effect property of monolayer to multilayer microstripes of an organic semiconductor.

The controllable growth of partially aligned monolayer to multilayer micrometer stripes was demonstrated by adjusting the pulling speed in a dip-coating process. The number of molecular layers decreases with the increasing pulling speed. A lower pulling speed yields mixed multilayers (3-9 monolayers). It is noteworthy that pure monolayer and bilayer microstripes over large areas can be obtained at high pulling speeds. The stripe morphology strongly depends on the pulling speed or the number of molecular layers. XRD and confocal fluorescence measurements manifest that monolayer stripes are amorphous, while multilayer stripes (> or = 2) consist of crystalline states. FET devices were fabricated on these stripes. Monolayer stripes failed to reveal a field effect due to their amorphous state. In contrast, multilayer stripes exhibit good field-effect behavior. This study provides useful information for future molecular design in controlling molecular architectures. The controllable growth from monolayer to multilayer offers a powerful experimental system for fundamental research into the real charge accumulation and transporting layers for OFETs.

Ultrathin alumina membranes for surface nanopatterning in fabricating quantum-sized nanodots.

Using ultrathin alumina membranes (UTAMs) as evaporation or etching masks large-scale ordered arrays of surface nanostructures can be synthesized on substrates. However, it is a challenge for this technique to synthesize quantum-sized surface structures. Here an innovative approach to prepare UTAMs with regularly arrayed pores in the quantum size range is reported. This new approach is based on a well-controlled pore-opening process and a modulated anodization process. Using UTAMs with quantum-sized pores for the surface patterning process, ordered arrays of quantum dots are synthesized on silicon substrates. This is the first time in realizing large-scale regularly arrayed surface structures in the quantum size range using the UTAM technique, which is an important breakthrough in the field of surface nanopatterning.