Plasmonic Annular Nanotrenches with 1 nm Nanogaps for Detection of SARS-CoV-2 Using SERS-Based Immunoassay.

This study represents the synthesis of a novel class of nanoparticles denoted as annular Au nanotrenches (AANTs). AANTs are engineered to possess embedded, narrow circular nanogaps with dimensions of approximately 1 nm, facilitating near-field focusing for detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) via a surface-enhanced Raman scattering (SERS)-based immunoassay. Notably, AANTs exhibited an exceedingly low limit of detection (LOD) of 1 fg/mL for SARS-CoV-2 spike glycoproteins, surpassing the commercially available enzyme-linked immunosorbent assay (ELISA) by 6 orders of magnitude (1 ng/mL from ELISA). To assess the real-world applicability, a study was conducted on 50 clinical samples using an SERS-based immunoassay with AANTs. The results revealed a sensitivity of 96% and a selectivity of 100%, demonstrating the significantly enhanced sensing capabilities of the proposed approach in comparison to ELISA and commercial lateral flow assay kits.

Rapid quantitative PCR equipment using photothermal conversion of Au nanoshell.

The emergence of infectious diseases worldwide necessitates rapid and precise diagnostics. Using gold nanoshells in the PCR mix, we harnessed their unique photothermal properties in the near-infrared regime to attain efficient heating, reaching ideal photothermal PCR cycle temperature profile. Our photothermal PCR method expedited DNA amplification while retaining its detection sensitivity. Combining photothermal quantitative PCR with real-time fluorometry and non-invasive temperature measurement, we could amplify the target DNA within just 25 min, with a minimum detectable DNA amount of 50 picograms. This innovation in photothermal qPCR, leveraging the photothermal properties of gold nanoshells, will pave the way for immediate point-of-care diagnostics of nucleic acid biomarkers.

Plasmonic Double-Walled Nanoframes with Face-to-Face Nanogaps for Strong SERS Activity.

A synthesis method for plasmonic double-walled nanoframes was developed, where single-walled truncated octahedral nanoframes with (111) open facets and (100) solid flat planes are nested in a core-shell manner. By applying multiple chemical toolkits to Au cuboctahedrons as a starting template, Au double-walled nanoframes with controllable face-to-face nanogaps were successfully synthesized in high homogeneity in size and shape. Importantly, when the gap distance between inner and outer flat walled frames became closer, augmentation of electromagnetic near-field focusing was achieved, leading to generation of hot-zones, which was verified by surface-enhanced Raman spectroscopy. The unique optical property of Au double-walled nanoframes with high structural intricacy was carefully investigated and the SERS substrates comprising Au double-walled nanoframes with the narrowest nanogaps exhibited much improved near-field enhancement toward strongly and/or weakly adsorbing analytes, allowing for gas phase detection in chemical warfare agents, which is a huge challenge in early warning systems.

Probing the optical near-field of plasmonic nano structure using scanning thermal microscopy.

Scanning thermal microscopy (SThM) enables to obtain thermal characteristic information such as temperature and thermal conductivity from the signals obtained by scanning a thermometer probe over a sample surface. Particularly, the precise control of the thermometer probe makes it possible to study near-field radiative heat transfer by measuring the near-field thermal energy, which implies that when light is used as a local heat source, photothermal energy can be detected from the optical near-field by approaching the probe in the near-field region. In this study, SThM is applied to generate sub-wavelength near-field optical image in the plasmonic grating coupler. Herein, by controlling the surface plasmon polariton generation, we show that the dominant component of SThM signal is from the optical response rather than the thermal response. The obtained near-field optical images have a spatial resolution of 40 nm and signal to noise ratio of up to 19.8. In addition, field propagation images in theZ-direction can be visualised with the precise control of the distance between the thermometer probe and the sample.

Plasmon-exciton couplings in the MoS2/AuNP plasmonic hybrid structure.

The understanding and engineering of the plasmon-exciton coupling are necessary to control the innovative optoelectronic device platform. In this study, we investigated the intertwined mechanism of each plasmon-exciton couplings in monolayer molybdenum disulfide (MoS2) and plasmonic hybrid structure. The results of absorption, simulation, electrostatics, and emission spectra show that interaction between photoexcited carrier and exciton modes are successfully coupled by energy transfer and exciton recombination processes. Especially, neutral exciton, trion, and biexciton can be selectively enhanced by designing the plasmonic hybrid platform. All of these results imply that there is another degree of freedom to control the individual enhancement of each exciton mode in the development of nano optoelectronic devices.

Three-dimensional nanoframes with dual rims as nanoprobes for biosensing.

Three-dimensional (3D) nanoframe structures are very appealing because their inner voids and ridges interact efficiently with light and analytes, allowing for effective optical-based sensing. However, the realization of complex nanoframe architecture with high yield is challenging because the systematic design of such a complicated nanostructure lacks an appropriate synthesis protocol. Here, we show the synthesis method for complex 3D nanoframes wherein two-dimensional (2D) dual-rim nanostructures are engraved on each facet of octahedral nanoframes. The synthetic scheme proceeds through multiple executable on-demand steps. With Au octahedral nanoparticles as a sacrificial template, sequential processes of edge-selective Pt deposition and inner Au etching lead to Pt octahedral mono-rim nanoframes. Then, adlayers of Au are grown on Pt skeletons via the Frank-van der Merwe mode, forming sharp and well-developed edges. Next, Pt selective deposition on both the inner and outer boundaries leads to tunable geometric patterning on Au. Finally, after the selective etching of Au, Pt octahedral dual-rim nanoframes with highly homogeneous size and shape are achieved. In order to endow plasmonic features, Au is coated around Pt frames while retaining their geometric shape. The resultant plasmonic dual-rim engraved nanoframes possess strong light entrapping capability verified by single-particle surface-enhanced Raman scattering (SERS) and show the potential of nanoprobes for biosensing through SERS-based immunoassay.

Nesting of multiple polyhedral plasmonic nanoframes into a single entity.

The development of plasmonic nanostructures with intricate nanoframe morphologies has attracted considerable interest for improving catalytic and optical properties. However, arranging multiple nanoframes in one nanostructure especially, in a solution phase remains a great challenge. Herein, we show complex nanoparticles by embedding various shapes of three-dimensional polyhedral nanoframes within a single entity through rationally designed synthetic pathways. This synthetic strategy is based on the selective deposition of platinum atoms on high surface energy facets and subsequent growth into solid platonic nanoparticles, followed by the etching of inner Au domains, leaving complex nanoframes. Our synthetic routes are rationally designed and executable on-demand with a high structural controllability. Diverse Au solid nanostructures (octahedra, truncated octahedra, cuboctahedra, and cubes) evolved into complex multi-layered nanoframes with different numbers/shapes/sizes of internal nanoframes. After coating the surface of the nanoframes with plasmonically active metal (like Ag), the materials exhibited highly enhanced electromagnetic near-field focusing embedded within the internal complicated rim architecture.

All-Hot-Spot Bulk Surface-Enhanced Raman Scattering (SERS) Substrates: Attomolar Detection of Adsorbates with Designer Plasmonic Nanoparticles.

Here we report a synthetic pathway toward Au truncated octahedral dual-rim nanoframes wherein two functional facets are formed including (1) eight hot nanogaps formed by hexagonal nanoframes embracing core circular nanorings for near-field focusing and (2) six flat squares that facilitate the formation of well-ordered arrays of nanoframes through self-assembly. The existence of intra-nanogaps in a single entity enables strong electromagnetic near-field focusing, allowing single-particle surface-enhanced Raman spectroscopy. Then, we built "all-hot-spot bulk SERS substrates" with those entities, wherein the presence of truncated terraces with high homogeneity in size and shape facilitate spontaneous self-assembly into a highly ordered and uniform superlattice, exhibiting a limit of detection of attomolar concentrations toward 2-naphthalenethiol, which is 6 orders lower than that of monorim counterparts. The observed low limit of detection originates from the combined synergic effect from both inter- and intraparticle coupling in a superlattice, which we dubbed "all-hot-spot bulk SERS substrates".

Plasmonic All-Frame-Faceted Octahedral Nanoframes with Eight Engraved Y-Shaped Hot Zones.

We report the synthesis of all-frame-faceted octahedral nanoframes containing eight Y-shaped hot zones in a single entity where electromagnetic near-field focusing can be maximized. To realize such state-of-the-art complex nanoframes, a series of multiple stepwise bottom-up processes were executed by exploiting Au octahedral nanoparticles as the initial template. By rationally controlling the chemical reactivity of different surface facets (i.e., vertexes, edges, and terraces), the Au octahedral nanoparticles went through controlled shape transformations, leading to Au-engraved nanoparticles wherein 24 edges wrap the octahedral Au nanoparticle core. Those edges were then selectively decorated with Pt, leading to the formation of eight Pt tripods in a single entity. After etching the central Au, 3D Pt tripod frame-faceted octahedral nanoframes were achieved with high integrity. By harnessing the obtained Pt nanoframes as a scaffold, AuAg alloy-based plasmonic all-frame-faceted nanoframes were obtained after the co-reduction of Ag and Au, which generated multiple hot zones within multiple surface intra-nanogaps, creating a single-particle, surface-enhanced Raman spectroscopy enhancer platform.

Biochar as a low-cost, eco-friendly, and electrically conductive material for terahertz applications.

We investigate conducting characteristics of biochar derived from the pyrolysis of a paper at terahertz frequencies. Paper is annealed under temperatures ranging from 600 to 1000 °C to modify structural and electrical properties. We experimentally observe that the terahertz conductivity increases above 102 S/m as the annealing temperature increases up to 800 °C. From structural characterization using energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, we confirm that more graphitic biochars are produced in high annealing temperature, in agreement with the improvement of terahertz conductivity. Our results show that biochar can be a highly promising candidate to be used in paper-based devices operating at terahertz frequencies.

Terahertz-driven polymerization of resists in nanoantennas.

Plasmon-mediated polymerization has been intensively studied for various applications including nanolithography, near-field mapping, and selective functionalization. However, these studies have been limited from the near-infrared to the ultraviolet regime. Here, we report a resist polymerization using intense terahertz pulses and various nanoantennas. The resist is polymerized near the nanoantennas, where giant field enhancement occurs. We experimentally show that the physical origin of the cross-linking is a terahertz electron emission from the nanoantenna, rather than multiphoton absorption. Our work extends nano-photochemistry into the terahertz frequencies.

Sub-10 nm feature chromium photomasks for contact lithography patterning of square metal ring arrays.

Advances in photolithographic processes have allowed semiconductor industries to manufacture smaller and denser chips. As the feature size of integrated circuits becomes smaller, there has been a growing need for a photomask embedded with ever narrower patterns. However, it is challenging for electron beam lithography to obtain <10 nm linewidths with wafer scale uniformity and a necessary speed. Here, we introduce a photolithography-based, cost-effective mask fabrication method based on atomic layer deposition and overhang structures for sacrificial layers. Using this method, we obtained sub-10 nm square ring arrays of side length 50 µm, and periodicity 100 µm on chromium film, on 1 cm by 1 cm quartz substrate. These patterns were then used as a contact-lithography photomask using 365 nm I-line, to generate metal ring arrays on silicon substrate.

Energy landscape scheme for an intuitive understanding of complex domain dynamics in ferroelectric thin films.

Fundamental understanding of domain dynamics in ferroic materials has been a longstanding issue because of its relevance to many systems and to the design of nanoscale domain-wall devices. Despite many theoretical and experimental studies, a full understanding of domain dynamics still remains incomplete, partly due to complex interactions between domain-walls and disorder. We report domain-shape-preserving deterministic domain-wall motion, which directly confirms microscopic return point memory, by observing domain-wall breathing motion in ferroelectric BiFeO3 thin film using stroboscopic piezoresponse force microscopy. Spatial energy landscape that provides new insights into domain dynamics is also mapped based on the breathing motion of domain walls. The evolution of complex domain structure can be understood by the process of occupying the lowest available energy states of polarization in the energy landscape which is determined by defect-induced internal fields. Our result highlights a pathway for the novel design of ferroelectric domain-wall devices through the engineering of energy landscape using defect-induced internal fields such as flexoelectric fields.