Optical Tweezing Terahertz Probing for a Single Metal Nanoparticle.

Recently, extensive research has been reported on the detection of metal nanoparticles using terahertz waves, due to their potential for efficient and nondestructive detection of chemical and biological samples without labeling. Resonant terahertz nanoantennas can be used to detect a small amount of molecules whose vibrational modes are in the terahertz frequency range with high sensitivity. However, the positioning of target molecules is critical to obtaining a reasonable signal because the field distribution is inhomogeneous over the antenna structure. Here, we combine an optical tweezing technique and terahertz spectroscopy based on nanoplasmonics, resulting in extensive controllable tweezing and sensitive detection at the same time. We observed optical tweezing of a gold nanoparticle and detected it with terahertz waves by using a single bowtie nanoantenna. Furthermore, the calculations confirm that molecular fingerprinting is possible by using our technique. This study will be a prestep of biomolecular detection using gold nanoparticles in terahertz spectroscopy.

Suppressed terahertz dynamics of water confined in nanometer gaps.

Nanoconfined waters exhibit low static permittivity mainly due to interfacial effects that span about one nanometer. The characteristic length scale may be much longer in the terahertz (THz) regime where long-range collective dynamics occur; however, the THz dynamics have been largely unexplored because of the lack of a robust platform. Here, we use metallic loop nanogaps to sharply enhance light-matter interactions and precisely measure real and imaginary THz refractive indices of nanoconfined water at gap widths ranging from 2 to 20 nanometers, spanning mostly interfacial waters all the way to quasi-bulk waters. We find that, in addition to the well-known interfacial effect, the confinement effect also contributes substantially to the decrease in the complex refractive indices of the nanoconfined water by cutting off low-energy vibrational modes, even at gap widths as large as 10 nanometers. Our findings provide valuable insights into the collective dynamics of water molecules which is crucial to understanding water-mediated processes.

Adaptive Gap-Tunable Surface-Enhanced Raman Spectroscopy.

Gap plasmon (GP) resonance in static surface-enhanced Raman spectroscopy (SERS) structures is generally too narrow and not tunable. Here, we present an adaptive gap-tunable SERS device to selectively enhance and modulate different vibrational modes via active flexible Au nanogaps, with adaptive optical control. The tunability of GP resonance is up to ∼1200 cm-1 by engineering gap width, facilitated by mechanical bending of a polyethylene terephthalate substrate. We confirm that the tuned GP resonance selectively enhances different Raman spectral regions of the molecules. Additionally, we dynamically control the SERS intensity through the wavefront shaping of excitation beams. Furthermore, we demonstrate simulation results, exhibiting the mechanical and optical properties of a one-dimensional flexible nanogap and their advantage in high-speed biomedical sensing. Our work provides a unique approach for observing and controlling the enhanced chemical responses with dynamic tunability.

Advancements of Intense Terahertz Field Focusing on Metallic Nanoarchitectures for Monitoring Hidden Interatomic Gas-Matter Interactions.

With the advancements of nanotechnology, innovative photonic designs coupled with functional materials provide a unique way to acquire, share, and respond effectively to information. It is found that the simple deposition of a 30 nm-thick palladium nanofilm on a terahertz (THz) metasurface chip with a 14 nm-wide effective nanogap of asymmetric materials and geometries allows the tracking of both interatomic and interfacial gas-matter interactions, including gas adsorption, hydrogenation (or dehydrogenation), metal phase changes, and unique water-forming reactions. Combinatorial analyses by simulation and experimental measurements demonstrate the distinct nanostructures, which leads to significant light-matter interactions and corresponding THz absorption in a real-time, highly repeatable, and reliable manner. The complex lattice dynamics and intrinsic properties of metals influenced by hydrogen gas exposure are also thoroughly examined using systematically controlled ternary gas mixture devices that mimic normal temperature and pressure. Furthermore, the novel degrees of freedom are utilized to analyze various physical phenomena, and thus, analytical methods that enable the tracking of unknown hidden stages of water-forming reactions resulting in water growth are introduced. A single exposure of the wave spectrum emphasizes the robustness of the proposed THz nanoscopic probe, bridging the gap between fundamental laboratory research and industry.

Trench Formation under the Tunable Nanogap: Its Depth Depends on Maximum Strain and Periodicity.

Metallic nanogaps have been studied for many years in the context of a significant amount of field enhancements. Nanogaps of macroscopic lengths for long-wave applications have attracted much interest, and recently one dimensional tunable nanogaps have been demonstrated using flexible PET substrates. For nanogaps on flexible substrates with applied tensile strain, large stress is expected in the vicinity of the gap, and it has been confirmed that several hundred nanometer-deep trenches form beneath the position of the nanogap because of this stress singularity. Here, we studied trench formation under nanogap structures using COMSOL Multiphysics 6.1. We constructed a 2D nanogap unit cell, consisting of gold film with a crack on a PDMS substrate containing a trench beneath the crack. Then, we calculated the von Mises stress at the bottom of the trench for various depths and spatial periods. Based on it, we derived the dependence of the trench depth on the strain and periodicity for various yield strengths. It was revealed that as the maximum tensile strain increases, the trench deepens and then diverges. Moreover, longer periods lead to larger depths for the given maximum strain and larger gap widths. These results could be applied to roughly estimate achievable gap widths and trench depths for stretchable zerogap devices.

Strain versus Tunable Terahertz Nanogap Width: A Simple Formula and a Trench below.

A flexible zerogap metallic structure is periodically formed, healing metal cracks on a flexible substrate. Zerogap is continuously tunable from nearly zero to one hundred nanometers by applying compressive strains on the flexible substrate. However, there have been few studies on how the gap width is related to the strain and periodicity, nor the mechanism of tunability itself. Here, based on atomic force microscopy (AFM) measurements, we found that 200 nm-deep nano-trenches are periodically generated on the polymer substrate below the zerogap owing to the strain singularities extant between the first and the second metallic deposition layers. Terahertz and visible transmission properties are consistent with this picture whereby the outer-bending polyethylene terephthalate (PET) substrate controls the gap size linearly with the inverse of the radius of the curvature.

Antenna-based reduced IR absorbers for high-performance microbolometers.

Absorbers for long-wavelength infrared (LWIR) are designed to have a reduced geometry fitted to a gold cross antenna and numerically studied. Compared to the square membrane geometry widely used in conventional microbolometers, the reduced geometry results in smaller thermal capacities of the vanadium dioxide (VO2) and silicon nitride (Si3N4) layers. However, near-field focusing by the cross antenna leads to a high LWIR absorption. Calculations show that the temperature change per incident energy increases with a decrease in the arm width, and the reduced absorber surpasses the square geometry for all incident angles and polarizations. The antenna-based reduced absorber studied here could serve as an alternative geometry for high-performance microbolometers.

Near-maximum microwave absorption in a thin metal film at the pseudo-free-standing limit.

Electromagnetic absorbers based on ultra-thin metallic film are desirable for many applications such as plasmonics, metamaterials, and long-wavelength detectors. A metallic film will achieve a maximum 50% of electromagnetic wave absorption, frequency independent, at a thickness defined by its conductivity, typically in the sub-Angstrom range for good metals if bulk conductivity is maintained throughout. This makes it extremely difficult to obtain substantial absorption from thin metal films, in contrast to 2D materials such as graphene. Luckily, however, from a practical point of view, metal conductivity is drastically reduced as the film becomes sub-100 nm, to make it a race between the thinnest possible metal thickness experimentally achievable vs the conductivity reduction. Here, we demonstrate a near-50% absorption at a gold film thickness of 6.5 nm, with conductivity much reduced from the bulk value, down to the range of 106 Siemens per meter. Studying the effect of the substrate thickness, we found that the common cover glass, with its thickness much smaller than the wavelength, achieves symmetric absorption of 44%, implying that a pseudo-free-standing limit is achieved. Our work may find applications in infrared sensing as in bolometers and biomedical sensing using microwaves.

Broadband high-performance terahertz polarizer based on a dense array of 5†nm gap slit antennas.

Critical factors for terahertz polarizers include broadband operation, high transmittance, and a good extinction ratio. In this paper, using a 5 nm-wide metallic slit array with a 200 nm periodicity as a wire grid polarizer, we achieved over 95% transmittance with an average extinction ratio of 40 dB, over the entire spectrum as defined by the terahertz time-domain spectroscopy (0.4 ∼ 2 THz). Theoretical calculations revealed that the slit array can show 100% transmission up to 5 THz, and wider bandwidths with a higher cutoff frequency can be achieved by reducing the slit periodicity. These results provide a novel approach for achieving a broadband THz polarizer and open a new path for seamless integration of the polarizers with nanophotonic applications.

Spatially Controlled Fabrication of Surface-Enhanced Raman Scattering Hot Spots through Photoinduced Dewetting of Silver Thin Films.

A well-designed narrow gap between noble metal nanostructures plays a prominent role in surface-enhanced Raman scattering (SERS) to concentrate electromagnetic fields at the local point, called a "hot spot". However, SERS-active substrate fabrication remains a substantial hurdle due to the high process cost and the difficulty of engineering efficient plasmonic hot spots at the target area. In this study, we demonstrate a simple photolithographic method for generating ultrasensitive SERS hot spots at desired positions. The solid-state dewetting of a Ag thin film (thickness of ∼10 nm) using a continuous-wave laser (∼1 MW/cm2) generates a closely packed assembly of hemispherical Ag nanoislands. Some of these nanoislands provide substantial plasmonic-field enhancement that is sufficient for single-molecule detection and plasmon-catalyzed chemical reaction. Such hot spot structures can be patterned on the substrate with a spatial resolution of better than 1 µm. In integrated analytical devices, the patterned SERS hot spots can be used as position-specific chemical-sensing elements.

Effective terahertz shielding properties of extreme graphene-silver nanowire surfaces investigated by nanoprobing.

In the terahertz (THz) electromagnetic wave regime, which has recently received great attention in the fields of communication and security, shielding of THz waves is a significant issue. Therefore, carbon-based nanostructures or polymer-carbon nanocomposites have been widely explored. Herein, significantly enhanced THz shielding efficiency is reported for silver nanowires coated with reduced graphene oxide (rGO) and nanoscale THz metamaterials, as compared to the cases without nanoscale metamaterials. Using a nanoslot-patterned metamaterial with strong resonances at certain frequencies, THz transmission in intensity is enhanced up to three orders of magnitude. Enhanced transmission by nanopatterns substantially increases the shielding performance to the external THz waves, even for ultrathin films (several tens of nanometers) produced by a simple spray of rGO (a few nm of flakes) on a complex random nanowire network. Excellent shielding performance is presented and the shielding mechanism is investigated by the nanoprobing configuration at the same time.

Topological Control of 2D Perovskite Emission in the Strong Coupling Regime.

Momentum space topology can be exploited to manipulate radiation in real space. Here we demonstrate topological control of 2D perovskite emission in the strong coupling regime via polaritonic bound states in the continuum (BICs). Topological polarization singularities (polarization vortices and circularly polarized eigenstates) are observed at room temperature by measuring the Stokes parameters of photoluminescence in momentum space. Particularly, in symmetry-broken structures, a very large degree of circular polarization (DCP) of ∼0.835 is achieved in the perovskite emission, which is the largest in perovskite materials to our knowledge. In the strong coupling regime, lower polariton modes shift to the low-loss spectral region, resulting in strong emission enhancement and large DCP. Our reciprocity analysis reveals that DCP is limited by material absorption at the emission wavelength. Polaritonic BICs based on 2D perovskite materials combine unique topological features with exceptional material properties and may become a promising platform for active nanophotonic devices.

Angstrom-Scale Active Width Control of Nano Slits for Variable Plasmonic Cavity.

Nanogap slits can operate as a plasmonic Fabry-Perot cavity in the visible and infrared ranges due to the gap plasmon with an increased wavenumber. Although the properties of gap plasmon are highly dependent on the gap width, active width tuning of the plasmonic cavity over the wafer length scale was barely realized. Recently, the fabrication of nanogap slits on a flexible substrate was demonstrated to show that the width can be adjusted by bending the flexible substrate. In this work, by conducting finite element method (FEM) simulation, we investigated the structural deformation of nanogap slit arrays on an outer bent polydimethylsiloxane (PDMS) substrate and the change of the optical properties. We found that the tensile deformation is concentrated in the vicinity of the gap bottom to widen the gap width proportionally to the substrate curvature. The width widening leads to resonance blueshift and field enhancement decrease. Displacement ratio ((width change)/(supporting stage translation)), which was identified to be proportional to the substrate thickness and slit period, is on the order of 10-5 enabling angstrom-scale width control. This low displacement ratio comparable to a mechanically controllable break junction highlights the great potential of nanogap slit structures on a flexible substrate, particularly in quantum plasmonics.

High sensitivity bolometers based on metal nanoantenna dimers with a nanogap filled with vanadium dioxide.

One critical factor for bolometer sensitivity is efficient electromagnetic heating of thermistor materials, which plasmonic nanogap structures can provide through the electric field enhancement. In this report, using finite element method simulation, electromagnetic heating of nanorod dimer antennas with a nanogap filled with vanadium dioxide (VO2) was studied for long-wavelength infrared detection. Because VO2 is a thermistor material, the electrical resistance between the two dimer ends depends on the dimer's temperature. The simulation results show that, due to the high heating ability of the nanogap, the temperature rise is several times higher than expected from the areal coverage. This excellent performance is observed over various nanorod lengths and gap widths, ensuring wavelength tunability and ultrafast operating speed, thereby making the dimer structures a promising candidate for high sensitivity bolometers.

Effective-zero-thickness terahertz slot antennas using stepped structures.

Metallic nanostructures play an essential role in electromagnetic manipulations due to the localization and enhancement of electromagnetic waves in nanogaps. Scaling down the dimensions of the gap, such as the gap width and the thickness, is an effective way to enhance light-matter interaction with colossal field enhancement. However, reducing the thickness below 10 nanometers still suffers from fabrication difficulty and unintended direct transmission through metals. Here, we fabricate effective-zero-thickness slot antennas by stepping metals in the vicinity of the gaps to confine electromagnetic waves in tiny volumes. We analyze and simulate terahertz transmission, and demonstrate the absorption enhancement of molecules in the slot antennas. Our fabrication technique provides a simple but versatile tool for maximum field enhancement and molecular sensing.

Ultra-Narrow Metallic Nano-Trenches Realized by Wet Etching and Critical Point Drying.

A metallic nano-trench is a unique optical structure capable of ultrasensitive detection of molecules, active modulation as well as potential electrochemical applications. Recently, wet-etching the dielectrics of metal-insulator-metal structures has emerged as a reliable method of creating optically active metallic nano-trenches with a gap width of 10 nm or less, opening a new venue for studying the dynamics of nanoconfined molecules. Yet, the high surface tension of water in the process of drying leaves the nano-trenches vulnerable to collapsing, limiting the achievable width to no less than 5 nm. In this work, we overcome the technical limit and realize metallic nano-trenches with widths as small as 1.5 nm. The critical point drying technique significantly alleviates the stress applied to the gap in the drying process, keeping the ultra-narrow gap from collapsing. Terahertz spectroscopy of the trenches clearly reveals the signature of successful wet etching of the dielectrics without apparent damage to the gap. We expect that our work will enable various optical and electrochemical studies at a few-molecules-thick level.

Topology-Changing Broadband Metamaterials Enabled by Closable Nanotrenches.

One of the most straightforward methods to actively control optical functionalities of metamaterials is to apply mechanical strain deforming the geometries. These deformations, however, leave symmetries and topologies largely intact, limiting the multifunctional horizon. Here, we present topology manipulation of metamaterials fabricated on flexible substrates by mechanically closing/opening embedded nanotrenches of various geometries. When an inner bending is applied on the substrate, the nanotrench closes and the accompanying topological change results in abrupt switching of metamaterial functionalities such as resonance, chirality, and polarization selectivity. Closable nanotrenches can be embedded in metamaterials of broadband spectrum, ranging from visible to microwave. The 99.9% extinction performance is robust, enduring more than a thousand bending cycles. Our work provides a wafer-scale platform for active quantum plasmonics and photonic application of subnanometer phenomena.

Phonon-Polaritons in Lead Halide Perovskite Film Hybridized with THz Metamaterials.

In this work, we demonstrated a phonon-polariton in the terahertz (THz) frequency range, generated in a crystallized lead halide perovskite film coated on metamaterials. When the metamaterial resonance was in tune with the phonon resonance of the perovskite film, Rabi splitting occurred due to the strong coupling between the resonances. The Rabi splitting energy was about 1.1 meV, which is larger than the metamaterial and phonon resonance line widths; the interaction potential estimation confirmed that the strong coupling regime was reached successfully. We were able to tune the polaritonic branches by varying the metamaterial resonance, thereby obtaining the dispersion curve with a clear anticrossing behavior. Additionally, we performed in situ THz spectroscopy as we annealed the perovskite film and studied the Rabi splitting as a function of the films' crystallization coverage. The Rabi splitting versus crystallization volume fraction exhibited a unique power-law scaling, depending on the crystal growth dimensions.

Copper-based etalon filter using antioxidant graphene layer.

Copper is a low-cost material compared to silver and gold, having high reflectivity in the near infrared spectral range as well as good electrical and thermal conductivity. Its properties make it a good candidate for metal-based low-cost multilayer thin-film devices and optical components. However, its high reflectance in the devices is reduced because copper is easily oxidized. Here, we suggest a copper-based Fabry-Perot optical filter consisting of a thin dielectric layer stacked between two copper films, which can realize low-cost production compared to a conventional silver-based etalon filter. The reduced performance due to the inherent oxidation of the copper surface can be overcome by passivating the copper films with monolayer graphene. The anti-oxidation of copper film is investigated by optical microscopy, x-ray photoelectron spectroscopy, and transmission measurement in UV-vi spectral ranges. Our results show that the graphene coating can be expanded for various metal-based optical devices in terms of anti-corrosion.

Fabrication of vertical van der Waals gap array using single-and multi-layer graphene.

Arrays of van der Waals gaps were manufactured by synthesizing the vertically aligned graphene layer stacked between two copper (Cu) catalytic films. The Cu-graphene-Cu laminated structure was obtained by directly synthesizing graphene on a patterned Cu film followed by depositing a second copper layer for optical measurements. The synthesis of graphene on the Cu surface was optimized by adjusting the synthesis temperatures and pre-annealing time using plasma enhanced chemical vapor deposition (PECVD). Resonant Raman spectroscopy measurements reveal that graphene can be synthesized on both bulk Cu foil and relatively thin Cu film under the same growth mechanism using PECVD. Structural and optical characterizations of the array of graphene van der Waals gaps were implemented by the transmission electron microscope and terahertz-time domain spectroscopy (THz-TDS). In THz-TDS, the measured THz amplitude transmitted through the graphene van der Waals gap slit array was constant regardless of the gap width determined by the number of graphene layers between the Cu thin films in a single slit. These results imply that the optical dielectric constant of graphene at THz frequencies in the out-of-plane direction is linearly proportional to the gap width. Our results of the manufacturing method can be adopted to investigate mechanical, electrical, and optical properties of other 2D materials such as h-BN, MoS2, and others. Furthermore, metal-graphene-metal structures with vertical orientations can be used in many electronic, optic, and optoelectronic applications.