Nanogap Arrays Research Articles

Customization of Nanogap Arrays Using Stereolithography and Nanoskiving for Surface-Enhanced Raman Scattering

Customization of Nanogap Arrays Using Stereolithography and Nanoskiving for Surface-Enhanced Raman Scattering

Charge-depletion-enhanced WSe2 quantum emitters on gold nanogap arrays with near-unity quantum efficiency

Charge-depletion-enhanced WSe2 quantum emitters on gold nanogap arrays with near-unity quantum efficiency

Origami nanogap electrodes for reversible nanoparticle trapping.

We present a facile desktop fabrication method for origami-based nanogap indium tin oxide (ITO) electrokinetic particle traps, providing a simplified approach compared to traditional lithographic techniques and effective trapping of nanoparticles. Our approach involves bending ITO thin films on optically transparent polyethylene terephthalate (PET), creating an array of parallel nanogaps. By strategically introducing weak points through cut-sharp edges, we successfully controlled the spread of nanocracks. A single crack spanning the constriction width and splitting the conductive layers forms a nanogap that can effectively trap small nanoparticles after applying an alternating electric potential across the nanogap. We analyze the conditions for reversible trapping and optimal performance of the nanogap ITO electrodes with optical microscopy and electrokinetic impedance spectroscopy. Our findings highlight the potential of this facile fabrication method for the use of ITO at active electro-actuated traps in microfluidic systems.

Detection of environmental nanoplastics via surface-enhanced Raman spectroscopy using high-density, ring-shaped nanogap arrays.

Micro- and nano-plastics (MNPs) are global contaminants of growing concern to the ecosystem and human health. In-the-field detection and identification of environmental micro- and nano-plastics (e-MNPs) is critical for monitoring the spread and effects of e-MNPs but is challenging due to the dearth of suitable analytical techniques, especially in the sub-micron size range. Here we show that thin gold films patterned with a dense, hexagonal array of ring-shaped nanogaps (RSNs) can be used as active substrates for the sensitive detection of micro- and nano-plastics by surface-enhanced Raman spectroscopy (SERS), requiring only small sample volumes and no significant sample preparation. By drop-casting 0.2-μL aqueous test samples onto the SERS substrates, 50-nm polystyrene (PS) nanoparticles could be determined via Raman spectroscopy at concentrations down to 1μg/mL. The substrates were successfully applied to the detection and identification of ∼100-nm polypropylene e-MNPs in filtered drinking water and ∼100-nm polyethylene terephthalate (PET) e-MNPs in filtered wash-water from a freshly cleaned PET-based infant feeding bottle.

Precisely constructing hybrid nanogap arrays via wet-transfer of dielectric metasurfaces onto a plasmonic mirror.

We propose a new method for fabricating hybrid metasurfaces by combining Mie and plasmonic resonances. Our approach involves obtaining an ultrasmooth gold film and separately structuring monocrystalline silicon (c-Si) nanoantenna arrays, which are then wet-transferred and finally immobilized onto the gold film. The experimental and simulation analysis reveals the importance of the native oxide layer of Si and demonstrates fascinating dispersion curves with nanogap resonances and bound states in the continuum. The localized field enhancements in the nanogap cavities result from the coupling between multipolar Mie resonances and their mirror images in the gold film. This effective method improves our understanding of hybrid modes and offers opportunities for developing active metasurfaces, such as depositing c-Si nanoantenna arrays onto stretchable polydimethylsiloxane substrates or electro-optic and piezoelectric sensitive lithium niobate films for potential applications in MEMS, LiDAR, and beyond.

Assembling Vertical Nanogap Arrays with Nanoentities for Highly Sensitive Electrical Biosensing.

Nanogap biosensors have emerged as promising platforms for detecting and measuring biochemical substances at low concentrations. Although the nanogap biosensors provide high sensitivity, low limit of detection (LOD), and enhanced signal strength, it requires arduous fabrication processes and costly equipment to obtain micro/nanoelectrodes with extremely narrow gaps in a controlled manner. In this work, we report the novel design and fabrication processes of vertical nanogap structures that can electrically detect and quantify low-concentration biochemical substances. Approximately 40 nm gaps are facilely created by magnetically assembling antibody-coated nanowires onto a nanodisk patterned between a pair of microelectrodes. Analyte molecules tagged with conductive nanoparticles are captured and bound to nanowires and bridge over the nanogaps, which consequently causes an abrupt change in the electrical conductivity between the microelectrodes. Using biotin and streptavidin as model antibodies and analytes, we demonstrated that our nanogap biosensors can effectively measure the protein analytes with the LOD of ∼18 pM. The outcome of this research could inspire the design and fabrication of nanogap devices and nanobiosensors, and it would have a broad impact on the development of microfluidics, biochips, and lab-on-a-chip architectures.

Ultra-dense plasmonic nanogap arrays for reorientable molecular fluorescence enhancement and spectrum reshaping.

Understanding interactions between molecular transition and intense electromagnetic fields confined by plasmon nanostructures is of great significance due to their huge potential in fundamental cavity quantum electrodynamics and practical applications. Here, we report reorientable plasmon-enhanced fluorescence leveraging the flexibilities in densely-packed gold nanogap arrays by template-assisted depositions. By finely adjusting the symmetry of the unit structure, arrays of nanogaps along two nearly-orthogonal axes can be tailored collectively with spacing down to sub-10 nm on a single chip, facilitating distinct "inter-cell" and "intra-cell" plasmon couplings. Through engineering two sets of nanogaps, the varying hybridization-induced plasmonic bonding modes lead to adjustable splitting of the fluorescence emission peak with a width up to 81 nm and narrowing of linewidths up to a factor of 3. Besides, polarization anisotropy with a ratio up to 63% is obtained on the basis of spectrally separated local hotspots with discrepant oscillation directions. The developed plasmonic nanogap array is envisaged to provide a promising chip-scale, cost-effective platform for advancing fluorescence-based detection and emission technologies in both classical and quantum regimes.

Multiple connected artificial synapses based on electromigrated Au nanogaps

Building an artificial synaptic device with multiple presynaptic inputs will be a significant step toward realization of sophisticated brain-inspired platforms for neuromorphic computing. However, an artificial synapse that can mimic functions of multiple synapses in a single device has not yet been well developed with existing electronic devices. Here, we experimentally implement the functions of multiple synapses in a single artificial synaptic device consisting of multiple connected nanogap electrodes. The “activation” technique, which is based on electromigration of metal atoms induced by a field emission current, was applied to the device to emulate the synaptic functions. We show that the device, upon application of activation, exhibits conductance changes in response to stimulation voltage, similar to the memory states of biological synapses. Several important synaptic responses—notably, short-term plasticity and long-term plasticity—were successfully demonstrated in multiple connected Au-nanogaps. For further application, a simple network was implemented using multi-input devices based on a two-terminal Au nanogap array, exhibiting the ability to classify the digital input vector pattern. These demonstrations pave the way for brain-inspired computing applications such as associative memory, pattern classification, and image recognition.

High-Throughput Fabrication of Triangular Nanogap Arrays for Surface-Enhanced Raman Spectroscopy.

Squeezing light into nanometer-sized metallic nanogaps can generate extremely high near-field intensities, resulting in dramatically enhanced absorption, emission, and Raman scattering of target molecules embedded within the gaps. However, the scarcity of low-cost, high-throughput, and reproducible nanogap fabrication methods offering precise control over the gap size is a continuing obstacle to practical applications. Using a combination of molecular self-assembly, colloidal nanosphere lithography, and physical peeling, we report here a high-throughput method for fabricating large-area arrays of triangular nanogaps that allow the gap width to be tuned from ∼10 to ∼3 nm. The nanogap arrays function as high-performance substrates for surface-enhanced Raman spectroscopy (SERS), with measured enhancement factors as high as 108 relative to a thin gold film. Using the nanogap arrays, methylene blue dye molecules can be detected at concentrations as low as 1 pM, while adenine biomolecules can be detected down to 100 pM. We further show that it is possible to achieve sensitive SERS detection on binary-metal nanogap arrays containing gold and platinum, potentially extending SERS detection to the investigation of reactive species at platinum-based catalytic and electrochemical surfaces.

Diversified plasmonic metallic nanostructures with high aspect ratio based on templated electrochemical deposition

Metallic high aspect ratio (HAR) nano-architectures provide new opportunities for a series of plasmonic devices due to their additional controllable degrees in height space compared to 2D patterns, but there is no efficient way that suitable for the rapid fabrication of large area HAR structures limited by the processing ability of traditional methods. Here in this work, we have developed a templated electrochemical deposition (ECD) method to fabricate various HAR metallic nano-structures for diversified plasmonic devices. The templated ECD method is based on the ECD filling of the nanopores that are fabricated by electron beam lithography. With this templated ECD method, numbers of HAR architectures including nanorods, nanofins and even mushroom-like structures, which have a line width as small as 100 nm and the aspect ratio up to 10:1, are established over a large scale. What is more, by simultaneously considering the designed layout and edge effect, sub 10 nm nanogap arrays are prepared, whose aspect ratio reaches 100:1 and the gap width reduces to 5 nm. Due to the extreme light confinement ability brought from Fabry–Perot resonance, the HAR nanogaps can be treated as a surface enhanced Raman scattering (SERS) substrate. Finite domain time difference simulation shows that fan-like 10 nm nanogap with a height of 700 nm has the largest light enhancement factor (EF). The configuration optimized nanogap is capable for the sensing of rhodamine 6G with a 10−9 M concentration. And the SERS EF of the nanogap is calculated to be 4 × 106, indicating the ultrasensitive molecular detection ability of the HAR nanogap. The templated ECD method not only brings a new chance for the construction of HAR metallic 3D structures, but also opens up a new horizon for the design of a series of plasmonic devices.

Electroluminescence of atoms in a graphene nanogap.

Here, we report light emission from single atoms bridging a graphene nanogap that emit bright visible light based on fluorescence of ionized atoms. Oxygen atoms in the gap shows a peak emission wavelength of 569 nm with a full width at half maximum (FWHM) of 208 nm. The energy states produced by these ionized oxygen atoms bridging carbon atoms in the gap also produce a large negative differential resistance (NDR) in the transport across the gap with the highest peak-to-valley current ratio (PVR = 45) and highest peak current density (~90 kA/cm2) ever reported in a solid-state tunneling device. While tunneling transport has been previously observed in graphene nanogaps, the bridging of ionized oxygen observed here shows a low excess current, leading to the observed PVR. On the basis of the highly reproducible light emission and NDR from these structures, we demonstrate a 65,536-pixel light-emitting nanogap array.

Wafer-Scale and Cost-Effective Manufacturing of Controllable Nanogap Arrays for Highly Sensitive SERS Sensing.

The metallic nanogap has been proved as an efficient architecture for surface-enhanced Raman scattering (SERS) applications. Although a lot of nanogap fabrication methods have been proposed in the last few decades, the economical and high-yield manufacturing of sub-10 nm gaps remains a challenge. Here, we present a convenient and cost-effective fabrication method for wafer-scale patterning of metallic nanogaps, which simply combines photolithographic metal patterning, swelling-induced nanocracking, and superimposition metal sputtering without requiring expensive nanofabrication equipment. By controlling the swelling time and metal deposition thickness, the gap size can be precisely defined, down to the sub-10 nm scale. Furthermore, we demonstrate that the fabricated nanogap array can be used as an excellent SERS substrate for molecule measurements and shows a high Raman enhancement factor of ∼108 and a high sensitivity for the detection of rhodamine 6G (R6G) molecules, even down to 10-14 M, indicating an extraordinary capability for single-molecule detection. Due to its high controllability and wafer-scale fabrication capability, this nanogap fabrication method offers a promising route for highly sensitive and economical SERS detections.

Preparation and Optical Properties of Polarization-Dependent Nano-Gap Array

Preparation and Optical Properties of Polarization-Dependent Nano-Gap Array

Local Cracking‐Induced Scalable Flexible Silicon Nanogaps for Dynamically Tunable Surface Enhanced Raman Scattering Substrates

AbstractSurface enhanced Raman scattering (SERS), as a promising and convenient analytical tool for molecule sensing, has turned out to be one of the most important applications of plasmonic nanostructures. However, its large‐area production, controllability, and adjustability remain significant challenges because of the weak control over the fabrication and spatial arrangement. Herein, a silicon nanogap array‐based flexible plasmonic substrate is developed, with capabilities of large‐area production, controllable arrangement, and width of nanogaps, by utilizing the standard microfabrication platform, and the fabricated flexible plasmonic substrate is further explored for dynamically tunable SERS for molecular sensing. After experimentally and theoretically optimizing the geometric designs of precursors, a 90 × 90 silicon nanogap array (over 1 cm × 1 cm) with a yield of about 99.74% is achieved. SERS is realized by depositing Au films onto the silicon nanogap. Dynamically tunable SERS is demonstrated by the thermally induced local stretch or contraction of silicon nanogaps, where the key parameters including Raman enhancement and sensitivity of the molecular sensor can be conveniently adjusted. These presented results significantly expand the scope of engineering opinions for flexible plasmonic nanostructures, which have many envisioned applications especially for environmental monitoring and biochemical detection.

Massively Parallel Arrays of Size-Controlled Metallic Nanogaps with Gap-Widths Down to the Sub-3-nm Level.

Metallic nanogaps (MNGs) are fundamental components of nanoscale photonic and electronic devices. However, the lack of reproducible, high-yield fabrication methods with nanometric control over the gap-size has hindered practical applications. A patterning technique based on molecular self-assembly and physical peeling is reported here that allows the gap-width to be tuned from more than 30nm to less than 3nm. The ability of the technique to define sub-3-nm gaps between dissimilar metals permits the easy fabrication of molecular rectifiers, in which conductive molecules bridge metals with differing work functions. A method is further described for fabricating massively parallel nanogap arrays containing hundreds of millions of ring-shaped nanogaps, in which nanometric size control is maintained over large patterning areas of up to a square centimeter. The arrays exhibit strong plasmonic resonances under visible light illumination and act as high-performance substrates for surface-enhanced Raman spectroscopy, with high enhancement factors of up to 3 × 108 relative to thin gold films. The methods described here extend the range of metallic nanostructures that can be fabricated over large areas, and are likely to find many applications in molecular electronics, plasmonics, and biosensing.

Plasmonic Hybrids of MoS2 and 10-nm Nanogap Arrays for Photoluminescence Enhancement

Monolayer MoS2 has attracted tremendous interest, in recent years, due to its novel physical properties and applications in optoelectronic and photonic devices. However, the nature of the atomic-thin thickness of monolayer MoS2 limits its optical absorption and emission, thereby hindering its optoelectronic applications. Hybridizing MoS2 by plasmonic nanostructures is a critical route to enhance its photoluminescence. In this work, the hybrid nanostructure has been proposed by transferring the monolayer MoS2 onto the surface of 10-nm-wide gold nanogap arrays fabricated using the shadow deposition method. By taking advantage of the localized surface plasmon resonance arising in the nanogaps, a photoluminescence enhancement of ~20-fold was achieved through adjusting the length of nanogaps. Our results demonstrate the feasibility of a giant photoluminescence enhancement for this hybrid of MoS2/10-nm nanogap arrays, promising its further applications in photodetectors, sensors, and emitters.

Boosting a sub-10 nm nanogap array by plasmon-triggered waveguide resonance

Gap-type metallic nanostructures are widely used in catalytic reactions, sensors, and photonics because the hotspot effect on these nanostructures supports giant local electromagnetic field enhancement. To achieve hotspots, researchers devote themselves to reducing gap distances, even to 1 nm. However, current techniques to fabricate such narrow gaps in large areas are still challenging. Herein, a new coupling way to boost the sub-10 nm plasmonic nanogap array is developed, based on the plasmon-triggered optical waveguide resonance via near-field coupling. This effect leads to an amplified local electromagnetic field within the gap regions equivalent to narrower gaps, which is evidenced experimentally by the surface-enhanced Raman scattering intensity of probed molecules located in the gap and the finite-difference time-domain numerical simulation results. This study provides a universal strategy to promote the performance of the existing hotspot configurations without changing their geometries.

Nanofluidic Immobilization and Growth Detection of Escherichia coli in a Chip for Antibiotic Susceptibility Testing.

Infections with antimicrobial resistant bacteria are a rising threat for global healthcare as more and more antibiotics lose their effectiveness against bacterial pathogens. To guarantee the long-term effectiveness of broad-spectrum antibiotics, they may only be prescribed when inevitably required. In order to make a reliable assessment of which antibiotics are effective, rapid point-of-care tests are needed. This can be achieved with fast phenotypic microfluidic tests, which can cope with low bacterial concentrations and work label-free. Here, we present a novel optofluidic chip with a cross-flow immobilization principle using a regular array of nanogaps to concentrate bacteria and detect their growth label-free under the influence of antibiotics. The interferometric measuring principle enabled the detection of the growth of Escherichia coli in under 4 h with a sample volume of 187.2 µL and a doubling time of 79 min. In proof-of-concept experiments, we could show that the method can distinguish between bacterial growth and its inhibition by antibiotics. The results indicate that the nanofluidic chip approach provides a very promising concept for future rapid and label-free antimicrobial susceptibility tests.

5 nm Nanogap Electrodes and Arrays by Super-resolution Laser Lithography.

The development of reliable, mass-produced, and cost-effective sub-10 nm nanofabrication technology leads to an unprecedented level of integration of photonic devices. In this work, we describe the development of a laser direct writing (LDW) lithography technique with ∼5 nm feature size, which is about 1/55 of the optical diffraction limit of the LDW system (405 nm laser and 0.9 NA objective), and the realization of 5 nm nanogap electrodes. This LDW lithography exhibits an attractive capability of well-site control and mass production of ∼5 × 105 nanogap electrodes per hour, breaking the trade-off between resolution and throughput in a nanofabrication technique. Nanosensing chips have been demonstrated with the as-obtained nanogap electrodes, where controllable surface enhancement Raman scattering of rhodamine 6G has been realized via adjusting the gap width and, especially, the applied bias voltages. Our results establish that such a low-cost and high-efficient lithography technology has great potential to fabricate compact integrated circuits and biochips.

Asymmetric transmission of light in hybrid waveguide-integrated plasmonic crystals on a silicon-on-insulator platform.

We demonstrate asymmetric transmission of light in hybrid waveguide-integrated plasmonic crystals where triangular silver islands create a regular array of nanogaps which couple to an underlying silicon-on-insulator optical waveguide. Up to 60% difference is observed between light transmission in the forward and backward directions. This asymmetric transmission of light is not caused by an external magnetic field or nonlinearity, but solely a consequence of the structure geometry.