Au Nanogap Research Articles

Controllable Construction of Aptamer-Modified Fe3O4@SiO2-Au Core-Shell-Satellite Nanocomposites with Surface-Enhanced Raman Scattering and Photothermal Properties and Their Effective Capture, Detection, and Elimination of Staphylococcus aureus.

The early monitoring and inactivation of bacteria are of crucial importance in preventing the further spread of foodborne pathogens. Staphylococcus aureus (S. aureus), a prototypical foodborne pathogen, is widely present in the natural environment and has the capability to trigger a range of diseases at low concentrations. In this work, we designed Fe3O4@SiO2-Au core-shell-satellite nanocomposites (NCs) modified with aptamer for efficient capture, high-sensitivity surface-enhanced Raman scattering (SERS) detection, and photothermal therapy (PTT) against S. aureus. Fe3O4@SiO2-Au NCs with tunable Au nanocrystal nanogaps were prepared. By combining the finite-difference time-domain (FDTD) method and experimental results, we studied the electric field distribution of Fe3O4@SiO2-Au under different Au nanogaps and ultimately obtained the optimal SERS substrate FSA-60. The modification of aptamer on the surfaces of FSA-60 could be used for the specific capture and selective detection of S. aureus, achieving a detection limit of as low as 50 cfu/mL. Furthermore, Apt-FSA-60 possessed excellent photothermal properties, demonstrating the strong photothermal killing ability against S. aureus. Therefore, Apt-FSA-60 is a promising high-sensitivity SERS substrate and efficient photothermal agent and is expected to be widely applied and promoted in future disease prevention and treatment.

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.

Trace level detection of melamine and cyanuric acid extracted from pet liquid food (milk) using a SERS Au nanogap substrate

This study reported an application of Au nanogap substrates for surface-enhanced Raman scattering (SERS) measurements to quantitatively analyze melamine and its derivative products at trace levels in pet liquid food (milk) combined with a waveband selection approach, namely variable importance in projection (VIP). Six different concentrations of melamine, cyanuric acid, and melamine combined with cyanuric acid were created, and SERS spectra were acquired from 550 to 1620cm−1. Detection was possible up to 200 pM for melamine-contaminated samples, and 400 pM concentration detection for other two groups. The VIP-PLSR models obtained correlation coefficient (R2) values of 0.997, 0.985, and 0.981, with root mean square error of prediction (RMSEP) values of 18.492 pM, 19.777 pM, and 15.124 pM for prediction datasets. Additionally, partial least square discriminant analysis (PLS-DA) was used to classify both pure and different concentrations of spiked samples. The results showed that the maximum classification accuracy for melamine was 100%, for cyanuric acid it was 96%, and for melamine coupled with cyanuric acid it was 95%. The results obtained clearly demonstrated that the Au nanogap substrate offers low-concentration, rapid, and efficient detection of hazardous additive chemicals in pet consuming liquid food.

Au nanogap SERS substrate for the carbaryl pesticide determination in juice and milk using chemomterics

Conventional spectroscopic methods like IR, and Raman are not very effective at detecting low levels of pesticides or harmful chemicals in food matrices. A quick, highly accurate approach that can identify pesticides present in different food products at lower levels must be developed in order to address this problem and ensure food safety. In this study, a highly sensitive and uniform wafer-scale Au nanogap surface-enhanced Raman spectroscopy (SERS) substrate was used for the quantitative analysis of carbaryl pesticide levels in standard solution, mango juice, and milk samples using chemometrics. Carbaryl was detected up to 3 ppb concentration levels for all three group of samples. However, due to the higher sensitivity, uniformity, and enhancement factors of the SERS substrate used in this investigation, the limit of detection (LOD) values for the standard solution, mango juice, and milk were 0.37 ppb, 0.57 ppb, and 0.15 ppb at 1380 cm−1, 1380 cm−1, and 1364 cm−1 wavenumber ranges. In order to predict different carbaryl concentrations (1, 2, 3, 4, and 5 ppb), the variable importance in projection (VIP) method combined with partial least squares regression (PLSR) and attained the coefficient of determination (R2) values of 0.994, 0.989, and 0.978 along with minimum root mean square error (RMSE) values of 0.112, 0.190, and 0.278 ppb for the prediction datasets. Furthermore, PLS-DA was able to distinguish between pure and adulterated samples with the highest classification accuracy of 100 % for a standard solution, and mango juice and 94.4 % for milk samples. Considering this, we can conclude that the SERS Au Nanogap substrate can rapidly and effectively detect carbaryl pesticides quantitatively and qualitatively in mango juice and milk.

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.

Radiofrequency Schottky Diodes Based on p-Doped Copper(I) Thiocyanate (CuSCN).

Schottky diodes based on inexpensive materials that can be processed using simple manufacturing methods are of particular importance for the next generation of flexible electronics. Although a number of high-frequency n-type diodes and rectifiers have been demonstrated, the progress with p-type diodes is lagging behind, mainly due to the intrinsically low conductivities of existing p-type semiconducting materials that are compatible with low-temperature, flexible, substrate-friendly processes. Herein, we report on CuSCN Schottky diodes, where the semiconductor is processed from solution, featuring coplanar Al–Au nanogap electrodes (<15 nm), patterned via adhesion lithography. The abundant CuSCN material is doped with the molecular p-type dopant fluorofullerene C60F48 to improve the diode’s operating characteristics. Rectifier circuits fabricated with the doped CuSCN/C60F48 diodes exhibit a 30-fold increase in the cutoff frequency as compared to pristine CuSCN diodes (from 140 kHz to 4 MHz), while they are able to deliver output voltages of >100 mV for a VIN = ±5 V at the commercially relevant frequency of 13.56 MHz. The enhanced diode and circuit performance is attributed to the improved charge transport across CuSCN induced by C60F48. The ensuing diode technology can be used in flexible complementary circuits targeting low-energy-budget applications for the emerging internet of things device ecosystem.

Carbaryl Pesticide Determination in Food Matrices by the Application of Surface-Enhanced Raman Scattering (Sers) AU Nano Gap Substrates in Conjunction with Chemometrics

Carbaryl Pesticide Determination in Food Matrices by the Application of Surface-Enhanced Raman Scattering (Sers) AU Nano Gap Substrates in Conjunction with Chemometrics

Sustainable Surface-Enhanced Raman Substrate with Hexagonal Boron Nitride Dielectric Spacer for Preventing Electric Field Cancellation at Au-Au Nanogap.

Nanogaps between Au nanoparticles and Au substrates are the simplest systems that generate extremely high electric fields at hotspots for surface-enhanced Raman spectroscopy (SERS). However, the electric field cancellation at the hotspots in the systems can cause the reduction of Raman signal when two metallic materials are physically contacted due to the low concentration of analytes. Here, we propose an atomically thin hexagonal boron nitride (h-BN) shielding layer for Au substrates, which can be used as an insulating spacer to prevent electrical shorts at nanogaps. Experimental investigation of the SERS effect combined with theoretical studies by finite-difference time-domain simulations demonstrate that the Au NP/h-BN/Au substrate structure has excellent performance in electrical short prevention, thus facilitating ultrasensitive Raman detection. The outstanding chemical and thermal stability of h-BN allow the efficient recycling of the SERS substrate by protecting the Au surface during the removal of Au NPs and molecular analytes by chemical and thermal processes.

Memory properties of electromigrated Au nanogaps to realize reservoir computing

The reservoir computing (RC) scheme, which employs the inherent computational capabilities of dynamical systems, is a key technology to implement artificial intelligence systems physically. Ensuring the nonlinear expansion of input data through the dynamics of physical systems is a necessary aspect of RC. Previously, we developed artificial synapses of Au nanogaps by using the “activation” technique, which allowed the implementation of synaptic functions such as short-term plasticity, long-term plasticity, and spike-timing-dependent plasticity. The activation technique is an electromigration-based method to control the tunnel resistance of nanogaps. In this study, the memory property of the Au nanogap, using activation for RC, was evaluated via short-term memory (STM) and parity check (PC) tasks. More specifically, memory capacity was introduced to evaluate the performance of the Au nanogap, defined as the sum of squares of the correlation between the outputs of RC and the teacher for delay D = 1 to 6. By utilizing the simple dynamics of short-term plasticity, the memory capacities of the STM and PC tasks were found to be 1.07 and 0.90, respectively, when 10 virtual nodes were used. This demonstrates that the dynamic process of the activation technique enables the Au nanogap-based reservoir to process information directly in the temporal domain. The experimental results can facilitate the development of compact devices to realize physical RC.

Tuning of polarized room-temperature thermal radiation based on nanogap plasmon resonance.

When a one-dimensional (1D) metal array is coupled to a planar metal mirror with a dielectric gap, localized plasmon resonance is excited inside the gap at a specific polarization of light in free space. Herein, we report on the completely polarized, mid-infrared thermal radiation that is released from gap plasmon resonators with a nanometer-thick dielectric. We fabricated nanogap plasmon resonators with 1D Au or Ni array of various widths (w) using laser interference lithography. An atomic layer deposition process was used to introduce a 10 nm-thick alumina gap between a 1D metal array and a planar metal mirror. It was observed that only for the Au nanogap plasmon resonators, high-amplitude absorption peaks that were attributed to gap plasmon modes with different orders appeared at discrete wavelengths in a polarization-resolved spectrum. In addition, all the pronounced peaks were gradually redshifted with increasing w. At w = 1.2-1.6 µm, the fundamental gap plasmon mode was tuned to the main wavelengths (8-9 µm) of thermal radiation at room temperature (e.g., ∼300 K), which led to polarization-selective camouflage against standard infrared thermal imaging. The results of electromagnetic simulations quantitatively agreed with the measured absorbance spectra in both peak wavelength and amplitude. We believe that these experimental efforts towards achieving radiation/absorption spectra tailored at mid-infrared wavelengths will be further exploited in thermal-radiation harnessed energy devices, spectroscopic sensors, and radiative coolers.

Gold nanogap-based artificial synapses

The basic building blocks for brain-inspired computing are neurons and their inter-cellular connections, called synapses. In this paper, we report artificial synapses composed of simple gold (Au) nanogaps that function using an electromigration-based method called “activation.” In the activation technique, metal-atom transport is induced by a field emission current, resulting in a change in gap separation. Synaptic functionalities, including long-term potentiation, long-term depression, and spike-timing-dependent plasticity, were successfully implemented in the electromigrated Au nanogaps using activation. Furthermore, the integration of four artificial synapses in a 2 × 2 array and image memorization were achieved with the Au nanogap-based artificial synapses. These results illustrate that electromigrated Au nanogaps hold promise as synaptic devices for bio-inspired computational systems.

Further enhancement of the near-field on Au nanogap dimers using quasi-dark plasmon modes

Metallic nanogap dimers are extremely useful for enhancing surface-enhanced Raman scattering and various nonlinear optical effects employing near-field enhancement effects induced by the localized surface plasmon resonance. However, the metallic nanogap dimers exhibit an intense light scattering due to the strong dipole-dipole interaction between two metallic nanostructures and, therefore, are not necessarily a structural design that exhibits the highest near-field enhancement due to the radiation loss. Here, we propose further enhancement of the near-field on metallic nanogap dimers using quasi-dark plasmon modes. By coupling with gold (Au) nanorods having the same plasmon resonant wavelength, but completely different sizes, a quasi-dark plasmon mode, which reduces the radiation loss slightly, is induced, resulting in the elongation of the plasmon dephasing time. As a result, the signal of surface-enhanced Raman scattering of crystal violet molecules adsorbed on the Au nanogap dimer is enhanced up to about three times as compared to that measured using the Au nanogap dimer without the Au nanorods. Scattering spectrum measurements as well as electromagnetic simulations were performed to clarify the mechanism for further enhancement of the near-field. The proposed coupled plasmonic system is expected to be advantageous, especially in enhancing nonlinear optical effects using plasmonic enhancement effects.

Sub‐10 nm Au–Ag Heterogeneous Plasmonic Nanogaps

AbstractControlling the formation of bimetallic heterogeneous nanogaps structures have many applications in the plasmonics and catalysis fields. Here, a simple and systematic method is developed to fabricate tunable and stable Au–Ag nanowire‐based plasmonic metamaterials. The sub‐10 nm Au–Ag bimetallic heterogeneous nanogaps with desirable optical properties are fabricated by a simple, ultrarapid, and robust nanoskiving technique. Compared to the monometallic linear Ag–Ag and Au–Au nanogaps, the Au–Ag bimetallic heterogeneous nanogaps exhibit remarkable surface enhanced Raman spectroscopy (SERS) enhancement properties due to the nanogaps between the adjacent Au/Ag nanowires, and the Ag/Au bimetallic composite film. In addition, 3D bimetallic heterogeneous nanogaps are built and produce much stronger electric fields than those of the 1D linear nanogaps. The sub‐10 nm Au–Ag heterogeneous nanogaps are promising to be used in SERS substrate, plasmon devices, catalysis, and printed electronics.

Synaptic behaviors of electromigrated Au nanogaps

Artificial electronic synapses or synaptic devices, which are capable of mimicking the functions of biological synapses in the human brain, are considered the basic building blocks for brain-inspired computing. Therefore, we investigated the emulation of synaptic functions in a simple Au nanogap. The synaptic functionality of neuromorphic hardware originates from a gradually modulated resistance. Previously, we investigated simple electromigration-based methods for controlling the tunnel resistance of nanogaps, called activation. In this study, a new type of artificial synaptic device based on planar Au nanogaps is demonstrated using a newly investigated activation procedure with voltage pulses. In the activation method with specific voltage pulses, the change in tunnel resistance of the Au nanogaps can be gradually controlled depending on the interval and amplitude of input voltage pulses. Moreover, Au inorganic synapses can emulate the synaptic functions of both short-term plasticity (STP) and long-term plasticity (LTP) characteristics. After the applied pulse is removed, the current decays rapidly at the beginning, followed by a gradual fade to a stable level. In addition, with repeated stimulations, the forgetting rate becomes decreases and the memory retention increases. Therefore, we observe an effect analogous to a memory transition from STP to LTP in biological systems. Our results may contribute to the development of highly functional artificial synapses and the further construction of neuromorphic computing architecture.

Ultralarge Area Sub-10 nm Plasmonic Nanogap Array by Block Copolymer Self-Assembly for Reliable High-Sensitivity SERS.

Effective surface enhancement of Raman scattering (SERS) requires strong near-field enhancement as well as effective light collection of plasmonic structures. To this end, plasmonic nanoparticle (NP) arrays with narrow gaps or sharp tips have been suggested as desirable structures. We present a highly dense and uniform Au nanoscale gap array enabled by the customized design of NP shape and arrangement employing block copolymer self-assembly. Block copolymer self-assembly in thin films offers uniform hexagonally packed nanopost template arrays over the entire surface of a 2 in. wafer. Conventional evaporative metal deposition over the nanotemplate surface allows precise geometric control and positional arrangement of metal NPs, constituting tunable, strong plasmonic near-field enhancement particularly at the "hot spots" near interparticular nanoscale gaps. Underlying field distribution has been investigated by a finite-difference time-domain simulation. In the detection of thiophenol, our Au nanogap array shows a remarkable enhancement of Raman intensity greater than ∼104, a standard deviation as small as 12.3% compared to that of the planar Au thin film. In addition, adenine biomolecules can be detected with a detection limit as low as 100 nM. Our approach proposes highly sensitive and reliable SERS on the basis of a scalable, low-cost bottom-up strategy.

Flexible nanogap polymer light-emitting diodes fabricated via adhesion lithography (a-Lith)

We report the development of coplanar green colour organic light-emitting diodes (OLEDs) based on asymmetric nanogap electrodes fabricated on different substrates including glass and plastic. Using adhesion lithography (a-Lith) we pattern Al and Au layers acting as the cathode and anode electrodes, respectively, separated by an inter-electrode distance of <15 nm with an aspect ratio of up to 106. Spin-coating the organic light-emitting polymer poly(9,9-dioctylfluorene-alt-bithiophene) (F8T2) on top of the asymmetric Al–Au nanogap electrodes results in green light-emitting nanogap OLEDs with promising operating characteristics. We show that the scaling of the OLED’s width from 4 to 200 mm can substantially improve the light output of the device without any adverse effects on the manufacturing yield. Furthermore, it is found that the light-emitting properties in the nanogap area differ from the bulk organic film, an effect attributed to confinement of the conjugated polymer chains in the nanogap channel. These results render a-Lith particularly attractive for low cost facile fabrication of nanoscale light-emitting sources and arrays on different substrates of arbitrary size.

Investigation of electromigration induced by field emission current flowing through Au nanogaps in ambient air

We developed a simple and controllable nanogap fabrication method called “activation.” In the activation technique, electromigration is induced by a field emission current passing through the nanogaps. Activation enables the electrical properties of Ni nanogaps in a vacuum to be controlled and is expected to be applicable to Au nanogaps even in ambient air. In this study, we investigated the activation properties of Au nanogaps in ambient air from a practical point of view. When activation was performed in ambient air, the tunnel resistance of the Au nanogaps decreased from over 100 TΩ to 3.7 MΩ as the preset current increased from 1 nA to 1.5 μA. Moreover, after activation in ambient air with a preset current of 500 nA, the barrier widths and heights of the Au nanogaps were estimated using the Simmons model to be approximately 0.5 nm and 3.3 eV, respectively. The extracted barrier height is smaller than that of 4.6 eV resulting from activation in a vacuum and much lower than the work function of bulk Au. This difference implies the presence of atmospherically derived moisture or contamination adsorbed on the nanogaps. These results suggest that activation can be utilized for Au nanogap fabrication even in ambient air.

Atomic-Layer-Deposition Assisted Formation of Wafer-Scale Double-Layer Metal Nanoparticles with Tunable Nanogap for Surface-Enhanced Raman Scattering

A simple high-throughput approach is presented in this work to fabricate the Au nanoparticles (NPs)/nanogap/Au NPs structure for surface enhanced Raman scattering (SERS). This plasmonic nanostructure can be prepared feasibly by the combination of rapid thermal annealing (RTA), atomic layer deposition (ALD) and chemical etching process. The nanogap size between Au NPs can be easily and precisely tuned to nanometer scale by adjusting the thickness of sacrificial ALD Al2O3 layer. Finite-difference time-domain (FDTD) simulation data indicate that most of enhanced field locates at Au NPs nanogap area. Moreover, Au NPs/nanogap/Au NPs structure with smaller gap exhibits the larger electromagnetic field. Experimental results agree well with FDTD simulation data, the plasmonic structure with smaller nanogap size has a stronger Raman intensity. There is highly strong plasmonic coupling in the Au nanogap, so that a great SERS effect is obtained when detecting methylene blue (MB) molecules with an enhancement factor (EF) over 107. Furthermore, this plasmonic nanostructure can be designed on large area with high density and high intensity hot spots. This strategy of producing nanoscale metal gap on large area has significant implications for ultrasensitive Raman detection and practical SERS application.

Memory operations in Au nanoparticle single-electron transistors with floating gate electrodes

Floating gate memory operations are demonstrated in a single-electron transistor (SET) fabricated by a chemical assembly using the Au nanogap electrodes and the chemisorbed Au nanoparticles. By applying pulse voltages to the control gate, phase shifts were clearly and stably observed both in the Coulomb oscillations and in the Coulomb diamonds. Writing and erasing operations on the floating gate memory were reproducibly observed, and the charges on the floating gate electrodes were maintained for at least 12 h. By considering the capacitance of the floating gate electrode, the number of electrons in the floating gate electrode was estimated as 260. Owing to the stability of the fabricated SET, these writing and erasing operations on the floating gate memory can be applied to reconfigurable SET circuits fabricated by a chemically assembled technique.

Integration of colloidal silicon nanocrystals on metal electrodes in single-electron transistor

We develop a facile process to integrate colloidal silicon nanocrystals (Si NCs) with metal electrodes in a single-electron transistor by self-assembly. Gold (Au) surface is modified by an amine-terminated self-assembled monolayer to have a positive potential. All-inorganic boron (B) and phosphorus (P) codoped Si NCs, with a negative surface potential and size-controllability, are selectively adsorbed on an amine-terminated Au surface by electrostatic attraction. We demonstrate the fabrication of SETs consisting of electroless-plated Au nanogap electrodes and codoped Si NCs using this process and observation of clear Coulomb diamonds at 9 K.