Search Results (8)

A variety of nanostructures capable of generating strong local electromagnetic fields (hot spots) in interaction with radiation have been under intensive investigation towards plasmonic applications in surface-enhanced Raman scattering (SERS), biosensing, broadband absorbers, thermophotovoltaics, photocatalysis, etc. In many cases, these nanostructures are formed on a surface or embedded into a near-surface layer of the dielectric substrate, making some part of the field dissipate into the bulk and not contribute to the desired plasmonic functionality. To reduce such losses, the interface between the metallic nanostructures and the dielectric environment should be engineered. In the current work, Au nanodiscs are fabricated on Si posts of very small diameter (pin-shaped structures), enabling them to decouple the strong optical near fields localized at the nanodiscs from the bulk Si substrate. The Si post diameter is optimized by adjusting the gas flow rates in reactive-ion etching, resulting in a minimum post diameter of 20 nm at the nanodisc interface. The effect of this diameter on the localized surface plasmon resonance of the nanodisc is investigated with linear optical spectroscopic measurements, where a significant spectral blue shift of the resonance band is noticed compared to similar discs formed on bulk Si surface. The experimental results are compared with modelling where a 3-fold increase in the electric field enhancement is demonstrated. The fabricated pin-shaped nanostructures are tested in SERS measurements showing a significant increase in the enhancement factor in the order of 10⁶. Thus, this work suggests a way of engineering 3D morphology to tune the substrate influence on the plasmonic properties of nanostructures and to develop efficient nanofabrication technologies. Full article

Anisotropic gold nanodiscs (AuNDs) possess unique properties, such as large flat surfaces and dipolar plasmon modes, which are ideal constituents for the fabrication of plasmonic assemblies for novel and emergent functions. In this report, we present the thermo-responsive assembly and thermo-dynamic behavior of AuNDs functionalized with methyl-hexa(ethylene glycol) undecane-thiol as a thermo-responsive ligand. Upon heating, the temperature stimulus caused a blue shift of the plasmon peak to form a face-to-face assembly of AuNDs due to the strong hydrophobic and van der Waals interactions between their large flat surfaces. Importantly, AuNDs allowed for the incorporation of the carboxylic acid-terminated ligand while maintaining their thermo-responsive assembly ability. With regard to their reversible assembly/disassembly behavior in the thermal cycling process, significant rate-independent hysteresis, which is related to their thermo-dynamics, was observed and was shown to be dependent on the carboxylic acid content of the surface ligands. As AuNDs have not only unique plasmonic properties but also high potential for attachment due to the fact of their flat surfaces, this study paves the way for the exploitation of AuNDs in the development of novel functional materials with a wide range of applications. Full article

To improve photoelectrochemical (PEC) water splitting, various ZnO nanostructures (nanorods (NRs), nanodiscs (NDs), NRs/NDs, and ZnO NRs decorated with gold nanoparticles) have been manufactured. The pure ZnO nanostructures have been synthesized using the successive ionic-layer adsorption and reaction (SILAR) combined with the chemical bath deposition (CBD) process at various deposition times. The structural, chemical composition, nanomorphological, and optical characteristics have been examined by various techniques. The SEM analysis shows that by varying the deposition time of CBD from 2 to 12 h, the morphology of ZnO nanostructures changed from NRs to NDs. All samples exhibit hexagonal phase wurtzite ZnO with polycrystalline nature and preferred orientation alongside (002). The crystallite size along (002) decreased from approximately 79 to 77 nm as deposition time increased from 2 to 12 h. The bandgap of ZnO NRs was tuned from 3.19 to 2.07 eV after optimizing the DC sputtering time of gold to 4 min. Via regulated time-dependent ZnO growth and Au sputtering time, the PEC performance of the nanostructures was optimized. Among the studied ZnO nanostructures, the highest photocurrent density (J_ph) was obtained for the 2 h ZnO NRs. As compared with ZnO NRs, the J_ph (7.7 mA/cm²) of 4 min Au/ZnO NRs is around 50 times greater. The maximum values of both IPCE and ABPE are 14.2% and 2.05% at 490 nm, which is closed to surface plasmon absorption for Au NPs. There are several essential approaches to improve PEC efficiency by including Au NPs into ZnO NRs, including increasing visible light absorption and minority carrier absorption, boosting photochemical stability, and accelerating electron transport from ZnO NRs to electrolyte carriers. Full article

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. Full article

We theoretically investigate a multi-resonant plasmonic metamaterial perfect absorber operating between 600 and 950 nm wavelengths. The presented device generates 100% absorption at two resonance wavelengths and delivers an ultra-narrow band (sub-20 nm) and high quality factor $(Q=44)$ resonance. The studied perfect absorber is a metal–insulator–metal configuration where a thin MgF${}_2$ spacer is sandwiched between an optically thick gold layer and uniformly patterned gold circular nanodisc antennas. The localized and propagating nature of the plasmonic resonances are characterized and confirmed theoretically. The origin of the perfect absorption is investigated using the impedance matching and critical coupling phenomenon. We calculate the effective impedance of the perfect absorber and confirm the matching with the free space impedance. We also investigate the scattering properties of the top antenna layer and confirm the minimized reflection at resonance wavelengths by calculating the absorption and scattering cross sections. The excitation of plasmonic resonances boost the near-field intensity by three orders of magnitude which enhances the interaction between the metamaterial surface and the incident energy. The refractive index sensitivity of the perfect absorber could go as high as $S=500$ nm/RIU. The presented optical characteristics make the proposed narrow-band multi-resonant perfect absorber a favorable platform for biosensing and contrast agent based bioimaging. Full article

Long-range interaction in regular metallic nanostructure arrays can provide the possibility to manipulate their optical properties, governed by the excitation of localized surface plasmon (LSP) resonances. When assembling the nanoparticles in an array, interactions between nanoparticles can result in a strong electromagnetic coupling for specific grating constants. Such a grating effect leads to narrow LSP peaks due to the emergence of new radiative orders in the plane of the substrate, and thus, an important improvement of the intensity of the local electric field. In this work, we report on the optical study of LSP modes supported by square arrays of gold nanodiscs deposited on an indium tin oxyde (ITO) coated glass substrate, and its impact on the surface enhanced Raman scattering (SERS) of a molecular adsorbate, the mercapto benzoic acid (4-MBA). We estimated the Raman gain of these molecules, by varying the grating constant and the refractive index of the surrounding medium of the superstrate, from an asymmetric medium (air) to a symmetric one (oil). We show that the Raman gain can be improved with one order of magnitude in a symmetric medium compared to SERS experiments in air, by considering the appropriate grating constant. Our experimental results are supported by FDTD calculations, and confirm the importance of the grating effect in the design of SERS substrates. Full article

Apolipoproteins are critical structural and functional components of lipoproteins, which are large supramolecular assemblies composed predominantly of lipids and proteins, and other biomolecules such as nucleic acids. A signature feature of apolipoproteins is the preponderance of amphipathic α-helical motifs that dictate their ability to make extensive non-covalent inter- or intra-molecular helix–helix interactions in lipid-free states or helix–lipid interactions with hydrophobic biomolecules in lipid-associated states. This review focuses on the latter ability of apolipoproteins, which has been capitalized on to reconstitute synthetic nanoscale binary/ternary lipoprotein complexes composed of apolipoproteins/peptides and lipids that mimic native high-density lipoproteins (HDLs) with the goal to transport drugs. It traces the historical development of our understanding of these nanostructures and how the cholesterol accepting property of HDL has been reconfigured to develop them as drug-loading platforms. The review provides the structural perspective of these platforms with different types of apolipoproteins and an overview of their synthesis. It also examines the cargo that have been loaded into the core for therapeutic and imaging purposes. Finally, it lays out the merits and challenges associated with apolipoprotein-based nanostructures with a future perspective calling for a need to develop “zip-code”-based delivery for therapeutic and diagnostic applications. Full article

Structural colour generation by nanoscale plasmonic structures is of major interest for non-bleaching colour printing, anti-counterfeit measures and decoration applications. We explore the physics of a two-metal plasmonic nanostructure consisting of metallic nanodiscs separated from a metallic back-reflector by a uniform thin polymer film and investigate the potential for vibrant structural colour in reflection. We demonstrate that light trapping within the nanostructures is the primary mechanism for colour generation. The use of planar back-reflector and polymer layers allows for less complex fabrication requirements and robust structures, but most significantly allows for the easy incorporation of two different metals for the back-reflector and the nanodiscs. The simplicity of the structure is also suitable for scalability. Combinations of gold, silver, aluminium and copper are considered, with wide colour gamuts observed as a function of the polymer layer thickness. The structural colours are also shown to be insensitive to the viewing angle. Structures of copper nanodiscs with an aluminium back-reflector produce the widest colour gamut. Full article