Tunable SERS Enhancement via Sub-nanometer Gap Metasurfaces.

Raman sensing is a powerful technique for detecting chemical signatures, especially when combined with optical enhancement techniques such as using substrates containing plasmonic nanostructures. In this work, we successfully demonstrated surface-enhanced Raman spectroscopy (SERS) of two analytes adsorbed onto gold nanosphere metasurfaces with tunable subnanometer gap widths. These metasurfaces, which push the bounds of previously studied SERS nanostructure feature sizes, were fabricated with precise control of the intersphere gap width to within 1 nm for gaps close to and below 1 nm. Analyte Raman spectra were measured for samples for a range of gap widths, and the surface-affected signal enhancement was found to increase with decreasing gap width, as expected and corroborated via electromagnetic field modeling. Interestingly, an enhancement quenching effect was observed below gaps of around 1 nm. We believe this to be one of the few studies of gap-width-dependent SERS for the subnanometer range, and the results suggest the potential of such methods as a probe of subnanometer scale effects at the interface between plasmonic nanostructures. With further study, we believe that tunable sub-nanometer gap metasurfaces could be a useful tool for the study of nonlocal and quantum enhancement-quenching effects. This could aid the development of optimized Raman-based sensors for a variety of applications.

Gate voltage and doping effects on near-field radiation heat transfer in plasmonic heterogeneous pairs of graphene and black phosphorene.

Plasmon coupling and hybridization in 2D materials plays a significant role for controlling light-matter interaction at the nanoscale. We present a near-field radiation heat transfer (NFRHT) between vertically separated graphene and black phosphorene sheets at different temperatures in nanoscale separations. Radiation exchange from the theory of fluctuation electrodynamics is modulated by the carrier density of graphene and phosphorene. Direct comparison of NFRHT black phosphorene-graphene to symmetric graphene-graphene radiation exchange can be as much as 4 times higher for the selected doping range in both armchair (AC) and zigzag (ZZ) orientations of BP. The strong NFRHT enhancement of the specific optical properties of the heterogenous 2D material is due to the strong coupling of propagating surface plasmon polaritons as demonstrated by the distribution of the heat transfer coefficient. We also demonstrate that the magnitude of the near-field radiation enhancement is found to acutely depend on the vacuum gap of the graphene and BP pair. Interestingly, for separation distances below 200 nm, the total near-field heat transfer between black phosphorene and graphene exceeds that between graphene and graphene by 5 times. The radiation enhancement can be further tuned based on the orientation, AC, and ZZ of black phosphorene. These results prominently enable dynamic control of the total NFRHT relying on tunable anisotropic characteristics of BP irrespective of graphene's optical conductivity. Furthermore, the heterogeneous pairs of 2D materials potentially provide alternative platforms to achieve beyond super-Planckian radiation.

The Role of Rayleigh-Wood Anomalies and Surface Plasmons in Optical Enhancement for Nano-Gratings.

We propose and report on the design of a 1-D metallo-dielectric nano-grating on a GaAs substrate. We numerically study the impact of grating period, slit and wire widths, and irradiating angle of incidence on the optical response. The optimal wire width, w = 160 nm, was chosen based on previous results from investigations into the influence of wire width and nano-slit dimensions on optical and electrical enhancements in metal-semiconductor-metal photodetectors. In this present project, resonant absorption and reflection modes were observed while varying the wire and nano-slit widths to study the unique optical modes generated by Rayleigh-Wood anomalies and surface plasmon polaritons. We observed sharp and diffuse changes in optical response to these anomalies, which may potentially be useful in applications such as photo-sensing and photodetectors. Additionally, we found that varying the slit width produced sharper, more intense anomalies in the optical spectrum than varying the wire width.

Plasmonic Au Array SERS Substrate with Optimized Thin Film Oxide Substrate Layer.

This work studies the effect of a plasmonic array structure coupled with thin film oxide substrate layers on optical surface enhancement using a finite element method. Previous results have shown that as the nanowire spacing increases in the sub-100 nm range, enhancement decreases; however, this work improves upon previous results by extending the range above 100 nm. It also averages optical enhancement across the entire device surface rather than localized regions, which gives a more practical estimate of the sensor response. A significant finding is that in higher ranges, optical enhancement does not always decrease but instead has additional plasmonic modes at greater nanowire and spacing dimensions resonant with the period of the structure and the incident light wavelength, making it possible to optimize enhancement in more accessibly fabricated nanowire array structures. This work also studies surface enhancement to optimize the geometries of plasmonic wires and oxide substrate thickness. Periodic oscillations of surface enhancement are observed at specific oxide thicknesses. These results will help improve future research by providing optimized geometries for SERS molecular sensors.

Tuning Infrared Plasmon Resonance of Black Phosphorene Nanoribbon with a Dielectric Interface.

We report on the tunable edge-plasmon-enhanced absorption of phosphorene nanoribbons supported on a dielectric substrate. Monolayer anisotropic black phosphorous (phosphorene) nanoribbons are explored for light trapping and absorption enhancement on different dielectric substrates. We show that these phosphorene ribbons support infrared surface plasmons with high spatial confinement. The peak position and bandwidth of the calculated phosphorene absorption spectra are tunable with low loss over a wide wavelength range via the surrounding dielectric environment of the periodic nanoribbons. Simulation results show strong edge plasmon modes and enhanced absorption as well as a red-shift of the peak resonance wavelength. The periodic Fabry-Perot grating model was used to analytically evaluate the absorption resonance arising from the edge of the ribbons for comparison with the simulation. The results show promise for the promotion of phosphorene plasmons for both fundamental studies and potential applications in the infrared spectral range.

Substrate Oxide Layer Thickness Optimization for a Dual-Width Plasmonic Grating for Surface-Enhanced Raman Spectroscopy (SERS) Biosensor Applications.

This work investigates a new design for a plasmonic SERS biosensor via computational electromagnetic models. It utilizes a dual-width plasmonic grating design, which has two different metallic widths per grating period. These types of plasmonic gratings have shown larger optical enhancement than standard single-width gratings. The new structures have additional increased enhancement when the spacing between the metal decreases to sub-10 nm dimensions. This work integrates an oxide layer to improve the enhancement even further by carefully studying the effects of the substrate oxide thickness on the enhancement and reports ideal substrate parameters. The combined effects of varying the substrate and the grating geometry are studied to fully optimize the device's enhancement for SERS biosensing and other plasmonic applications. The work reports the ideal widths and substrate thickness for both a standard and a dual-width plasmonic grating SERS biosensor. The ideal geometry, comprising a dual-width grating structure atop an optimal SiO2 layer thickness, improves the enhancement by 800%, as compared to non-optimized structures with a single-width grating and a non-optimal oxide thickness.

Calculated thickness dependent plasmonic properties of gold nanobars in the visible to near-infrared light regime.

Metallic, especially gold, nanostructures exhibit plasmonic behavior in the visible to near-infrared light range. In this study, we investigate optical enhancement and absorption of gold nanobars with different thicknesses for transverse and longitudinal polarizations using finite element method simulations. This study also reports on the discrepancy in the resonance wavelengths and optical enhancement of the sharp-corner and round-corner nanobars of constant length 100 nm and width 60 nm. The result shows that resonance amplitude and wavelength have strong dependences on the thickness of the nanostructure as well as the sharpness of the corners, which is significant since actual fabricated structure often have rounded corners. Primary resonance mode blue-shifts and broadens as the thickess increases due to decoupling of charge dipoles at the surface for both polarizations. The broadening effect is characterized by measuring the full width at half maximum of the spectra. We also present the surface charge distribution showing dipole mode oscillations at resonance frequency and multimode resonance indicating different oscillation directions of the surface charge based on the polarization direction of the field. Results of this work give insight for precisely tuning nanobar structures for sensing and other enhanced optical applications.

Thermoplasmonics: quantifying plasmonic heating in single nanowires.

Plasmonic absorption of light can lead to significant local heating in metallic nanostructures, an effect that defines the subfield of thermoplasmonics and has been leveraged in diverse applications from biomedical technology to optoelectronics. Quantitatively characterizing the resulting local temperature increase can be very challenging in isolated nanostructures. By measuring the optically induced change in resistance of metal nanowires with a transverse plasmon mode, we quantitatively determine the temperature increase in single nanostructures with the dependence on incident polarization clearly revealing the plasmonic heating mechanism. Computational modeling explains the resonant and nonresonant contributions to the optical heating and the dominant pathways for thermal transport. These results, obtained by combining electronic and optical measurements, place a bound on the role of optical heating in prior experiments and suggest design guidelines for engineered structures meant to leverage such effects.

Dark plasmons in hot spot generation and polarization in interelectrode nanoscale junctions.

Nanoscale gaps between adjacent metallic nanostructures give rise to extraordinarily large field enhancements, known as "hot spots", upon illumination. Incident light with the electric field polarized across the gap (along the interparticle axis) is generally known to induce the strongest surface enhanced Raman spectroscopy (SERS) enhancements. However, here we show that, for a nanogap located within a nanowire linking extended Au electrodes, the greatest enhancement and resulting SERS emission occurs when the electric field of the incident light is polarized along the gap (transverse to the interelectrode axis). This surprising and counterintuitive polarization dependence results from a strong dipolar plasmon mode that resonates transversely across the nanowire, coupling with dark multipolar modes arising from subtle intrinsic asymmetries in the nanogap. These modes give rise to highly reproducible SERS enhancements at least an order of magnitude larger than the longitudinal modes in these structures.

Nanogap structures: combining enhanced Raman spectroscopy and electronic transport.

Surface-enhanced Raman spectroscopy (SERS) is an experimental tool for accessing vibrational and chemical information, down to the single molecule level. SERS typically relies on plasmon excitations in metal nanostructures to concentrate the incident radiation and to provide an enhanced photon density of states to couple emitted radiation to the far field. Many common SERS platforms involve metal nanoparticles to generate the required electromagnetic enhancements. Here we concentrate on an alternative approach, in which the relevant plasmon excitations are supported at a truly nanoscale gap between extended electrodes, rather than discrete subwavelength nanoparticles. The ability to fabricate precise gaps on demand, and in some cases to tune the gap size in situ, combined with the additional capability of simultaneous electronic transport measurements of the nanogap, provides access to information not previously available in standard SERS. We summarize the rich plasmonic physics at work in these extended systems and highlight the recent state of the art including tip-enhanced Raman spectroscopy (TERS) and the application of mechanical break junctions and electromigrated junctions. We describe in detail how we have performed in situ gap-enhanced Raman measurements of molecular-scale junctions while simultaneously subjecting these structures to electronic transport. These extended electrode structures allow us to study the pumping of vibrational modes by the flow of tunneling electrons, as well as the shifting of vibrational energies due to the applied bias. These experiments extend SERS into a tool for examining fundamental processes of dissipation, and provide insight into the mechanisms behind SERS spectral diffusion. We conclude with a brief discussion of future directions.