Gold Nanohole Research Articles

Direct fabrication of rough gold nanoholes and investigation of their second-harmonic generation

In this study, we introduce a simple and cost-effective technique called one-photon absorption-based direct laser writing (OPA-based DLW) to directly fabricate noncentrosymmetric gold nanoholes (Au NHs). This technique relies on the optically induced local thermal effect at the focusing spot using a 532 nm excitation wavelength, which induces the evaporation of the Au thin film and thereby creating metal NHs. By controlling the exposure doses, including fabrication powers and writing velocities, we achieve Au NHs with small sizes around 300 nm and a periodicity of 500 nm. Moreover, due to the non-uniform heat transfer in an imperfectly flat Au film, the formed NHs lack perfect circularity, showing roughness and asymmetry. Thanks to this irregular shape of Au NHs, second-harmonic generation (SHG) signals are generated. This nonlinear signal can be amplified thanks to near electric field intensity enhancement at the borders of the holes. By moving the focusing spot, this DLW method allows us to fabricate any desired two-dimensional patterns, which exhibit SHG signals. This ability could be advantageous for applications in optical data storage and nonlinear imaging.

Angle-Resolved Fluorescence of a Dye Coupled to a Plasmonic Nanohole Array

Gold nanohole arrays are periodic metasurfaces that are gathering huge interest in biosensing applications. The bi-dimensional grating-like structure defines their plasmonic response, together with the corresponding mode of angular dispersion. These properties can be used to investigate the interaction processes with the fluorescence features of a properly chosen emitting molecule. By employing a custom gold nanohole array alongside a commercial organic dye, we conducted an accurate angle-resolved optical characterization resorting to fluorescence, reflectance, and transmittance spectra. The coupling between the plasmonic modes and the fluorescence features was then identified as a modification of the dye fluorescence signal in terms of both spectral redistribution and enhancement. By carefully analyzing the results, different measurement efficiencies can be identified, depending on the set-up configuration, to be properly engineered for sensitivity maximization in plasmon-enhanced fluorescence-based applications.

Nanofabrication Process Scale-Up via Displacement Talbot Lithography of a Plasmonic Metasurface for Sensing Applications

The selection of an affordable method to fabricate plasmonic metasurfaces needs to guarantee complex control over both tunability and reproducibility of their spectral and morphological properties, making plasmonic metasurfaces suitable for integration into different sensing devices. Displacement Talbot lithography could be a valid solution thanks to the limited fabrication steps required, also providing the highly desired industrial scalability. Fabricated plasmonic metasurfaces are represented by a gold nanohole array on a glass substrate based on a triangular pattern. Scanning electron microscopy measurements have been recorded, showing the consistency of the surface features with the optimized design parameters. Reflectance and transmittance measurements have also been carried out to test the reliability and standardization of the metasurface’s optical response. Furthermore, these plasmonic metasurfaces have also been successfully tested for probing refractive index variations in a microfluidic system, paving the way for their use in sensitive, real-time, label-free, and multiplexing detection of bio-molecular events.

Convergence and Performance Analysis of a Particle Swarm Optimization Algorithm for Optical Tuning of Gold Nanohole Arrays.

Gold nanohole arrays, hybrid metal/dielectric metasurfaces composed of periodically arranged air holes in a thick gold film, exhibit versatile support for both localized and propagating surface plasmons. Leveraging their capabilities, particularly in surface plasmon resonance-oriented applications, demands precise optical tuning. In this study, a customized particle swarm optimization algorithm, implemented in Ansys Lumerical FDTD, was employed to optically tune gold nanohole arrays treated as bidimensional gratings following the Bragg condition. Both square and triangular array dispositions were considered. Convergence and evolution of the particle swarm optimization algorithm were studied, and a mathematical model was developed to interpret its outcomes.

Tip-based Lithography with a Sacrificial Layer.

The fabrication of a highly controlled gold (Au) nanohole (NH) array via tip-based lithography is improved by incorporating a sacrificial layer-a tip-crash buffer layer. This inclusion mitigates scratches during the nano-indentation process by employing a 300nm thick poly(methyl methacrylate) layer as a sacrificial layer on top of the Au film. Such a precaution ensures minimal scratches on the Au film, facilitating the creation of sub-50nm Au NHs with a 15nm gap between the Au NHs. The precision of this method exceeds that of fabricating Au NHs without a sacrificial layer. Demonstrating its versatility, this Au NH array is utilized in two distinct applications: as a dry etching mask to form a molybdenum disulfide hole array and as a catalyst in metal-assisted chemical etching, resulting in conical-shaped silicon nanostructures. Additionally, a significant electric field is generated when Au nanoparticles (NPs) are placed within the Au NHs. This effect arises from coupling electromagnetic waves, concentrated by the Au NHs and amplified by the Au NPs. A notable result of this configuration is the enhancement factor of surface-enhanced Raman scattering, which is an order of magnitude greater than that observed with just Au NHs and Au NPs alone.

Deep learning-driven forward and inverse design of nanophotonic nanohole arrays: streamlining design for tailored optical functionalities and enhancing accessibility.

In nanophotonics, nanohole arrays (NHAs) are periodic arrangements of nanoscale apertures in thin films that provide diverse optical functionalities essential for various applications. Fully studying NHAs' optical properties and optimizing performance demands understanding both materials and geometric parameters, which presents a computational challenge due to numerous potential combinations. Efficient computational modeling is critical for overcoming this challenge and optimizing NHA-based device performance. Traditional approaches rely on time-consuming numerical simulation processes for device design and optimization. However, using a deep learning approach offers an efficient solution for NHAs design. In this work, a deep neural network within the forward modeling framework accurately predicts the optical properties of NHAs by using device structure data such as periodicity and hole radius as model inputs. We also compare three deep learning-based inverse modeling approaches-fully connected neural network, convolutional neural network, and tandem neural network-to provide approximate solutions for NHA structures based on their optical responses. Once trained, the DNN accurately predicts the desired result in milliseconds, enabling repeated use without wasting computational resources. The models are trained using over 6000 samples from a dataset obtained by finite-difference time-domain (FDTD) simulations. The forward model accurately predicts transmission spectra, while the inverse model reliably infers material attributes, lattice geometries, and structural parameters from the spectra. The forward model accurately predicts transmission spectra, with an average Mean Squared Error (MSE) of 2.44 × 10-4. In most cases, the inverse design demonstrates high accuracy with deviations of less than 1.5 nm for critical geometrical parameters. For experimental verification, gold nanohole arrays are fabricated using deep UV lithography. Validation against experimental data demonstrates the models' robustness and precision. These findings show that the trained DNN models offer accurate predictions about the optical behavior of NHAs.

Surface-enhanced Raman spectroscopy with single cell manipulation by microfluidic dielectrophoresis.

When exposed to an alternating current (AC) electric field, a polarized microparticle is moved by the interaction between the voltage-induced dipoles and the AC electric field under dielectrophoresis (DEP). The DEP force is widely used for manipulation of microparticles in diverse practical applications such as 3D manipulation, sorting, transfer, and separation of various particles such as living cells. In this study, we propose the integration of surface-enhanced Raman spectroscopy (SERS), an extremely sensitive and versatile technique based on the Raman scattering of molecules supported by nanostructured materials, with DEP using a microfluidic device. The microfluidic device combines microelectrodes with gold nanohole arrays to characterize the electrophysiological and biochemical properties of biological cells. The movement of particles, which varies depending on the electrical properties such as conductivity and permittivity of particles, can be manipulated by the cross-frequency change. For proof of concept, Raman spectroscopy using the DEP-SERS integration was performed for polystyrene beads and biological cells and resulted in an improved signal-to-noise ratio by determining the direction of the DEP force applied to the cells with respect to the applied AC power and collecting them on the nanohole arrays. The result illustrates the potential of the concept for simultaneously examining the electrical and biochemical properties of diverse chemical and biological microparticles in the microfluidic environment.

Impact of Optical Cavity on Refractive Index Sensitivity of Gold Nanohole Arrays.

Refractive index sensing based on surface plasmon resonance (SPR) is a highly efficient label-free technique for biomolecular detection. The performance of this method is defined by the dielectric properties of a sensing layer and its structure. Nanohole arrays in thin metal films provide good refractive index sensitivity but often suffer from a large resonance linewidth, which limits their broad practical application in biosensorics. Coupling the broad plasmon modes to sharp resonances can reduce the peak widths, but at the same time it can also degrade the sensitivity. Here, we use Finite-Difference Time Domain simulations to study the factors affecting the sensing performance of gold-silica-gold optical cavities with nanohole arrays in the dielectric and top metal layers. We demonstrate that by tuning resonator size and inter-hole spacing, the performance of the biosensor can be optimized and the figure of merit of the order of 5-7 is reached.

Novel insight into the physics of short-range ordered nanoholes: Newly defined lattice model and transmittance response related to lattice parameters and ordering evolution

This paper presents unforeseen conceptualization, methods and results on the physics of short-range ordered (SRO) gold nanohole (NH) distributions, fabricated by a recent protocol developed by the authors. The straightforward extension to SRONHs of the existing knowledge about periodic NH arrays is confuted and an alternative interpretative picture is proposed and discussed based on three main advancements. First, it is set up a so-called short-range lattice (SR-Lat) method to rigorously and fully characterize the coverage-dependent short-range ordering through the determination of local coordination and periodicity length (aSR) of the NH arrangement. Second, it is demonstrated the failure of the common assumption that the average center-to-center distance of nearest neighbor colloids/nanoholes (dNN) is the characteristic length-scale of SRONHs and aSR is set as the proper periodicity parameter. Third, a predictive relationship is formulated between the wavelength of the propagating plasmon modes and aSR that highlights inherent differences with respect to periodic NHs.The presented results lay rigorous foundation for studying systems with correlated diosrdering in general and for making predictions useful not only in design and applications of SRONHs, but also on the surface physics in the photonics and sensing fields.

Achieving high sensitivity by adding rings to a plasmonic metasurface with nano-holes

This report demonstrates a subwavelength plasmonic metasurface for a refractive index sensor at near-infrared (NIR) wavelengths. This sensor includes a two-dimensional periodic array of gold nano-rings and nano-holes in a gold film. The structure's potential for high-sensitivity sensing in reflection configuration has been demonstrated. We use a TiN layer in this structure. It prevents light transmission from the resonators, making the transmission spectrum near zero and causing a deeper reflection dip. This sensor can be suitable for biosensing applications like poliovirus sensing. Generally, high sensitivity is obtained for poliovirus of over 817 nm/RIU. It is shown that making ledges around nano-holes increases the resonance wavelength shift and, therefore, the sensitivity by more than 33 times.

Gold nanohole arrays with ring-shaped silver nanoparticles for highly efficient plasmon-enhanced fluorescence

To enhance the interaction between electromagnetic fields and reduce photoluminescence (PL) lifetime in plasmon-enhanced fluorescence, this study presents a novel approach involving the fabrication of gold (Au) nanohole arrays (ANA) decorated with ring-shaped silver nanoparticles (AgNPs) on a silicon-dioxide (SiO2)/silver (Ag) substrate. The surface plasmon resonance coupling in terms of the PL reactions of ANA substrates with and without ring-shaped AgNPs is investigated via experiments and numerical simulations. The remarkable enhancement of PL intensity of the proposed substrate is attributed to increased absorption, which enables the tuning of surface-enhanced electromagnetic fields. Specifically, the Raman signal of rhodamine 6G (R6G) dye and the PL intensity of 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) molecules are significantly enhanced 3.7 and 2.2 times, respectively, compared to those of the bare ANA substrate. Meanwhile, the PL lifetime is reduced by 46.15%. These results confirm that ANAs decorated with ring-shaped AgNPs can significantly improve plasmon-enhanced fluorescence. The findings presented herein demonstrate the potential to revolutionize biosensing, imaging, and photonics.

Multiple Features-Based Improved Nanohole Array Plasmonic Biosensor

In recent years, gold nanohole array-based biosensors have gained tremendous attention due to their high sensitivity, label-free biosensing, and real-time simultaneous multiple analyte detection capabilities. However, nanohole array-based biosensors using conventional sensing methods lack the resolution of traditional surface plasmon resonance (SPR) sensors. In this work, we present numerical methods utilizing multiple peaks of these biosensors’ transmission spectra to achieve higher sensitivity and lower detection limits. Using finite-difference time-domain (FDTD) simulations, we compared the sensing performance of the proposed numerical methods to traditional peak-shift and spectral integration methods. We added noise to the transmission spectra to simulate a realistic system and determined the change in the performance. We also optimized the geometrical parameters of the gold nanohole array for optimal sensing performance. Finally, we applied the proposed method to two critical real-life biosensing applications and reported the sensitivity and limit of detection (LOD). The proposed numerical methods show much higher sensitivity and lower detection limits than the traditional techniques. The observed detection limits are as low as <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\sim {2} \times {10}^{-{6}}$ </tex-math></inline-formula> refractive index unit changes near the surface. The proposed methods can be utilized for any sensing systems that employ transmission spectra and will outperform traditional methods if there are multiple peaks present in the transmission spectra.

Plasmonic metasurface enhanced by nanobumps for label-free biosensing of lung tumor markers in serum

Plasmonic metasurface biosensing has excellent potential in label-free detection of tumor biomarkers. In general, a variety of plasmonic metasurface nanofabrication leads to various degree of metallic surface roughness. However, the metasurface roughness effects on plasmonic sensing of tumor markers have been barely reported. Here we fabricate high-roughness (HR) gold nanohole metasurfaces with nanobumps and investigate their biosensing in comparison with the low-roughness (LR) counterparts. The HR metasurfaces demonstrate the surface sensitivity of multilayer polyelectrolyte molecules, which is 57.0% higher than the LR ones. The HR metasurfaces also illuminate higher immunoassay sensitivity to multiple lung cancer biomarkers, including carcinoembryonic antigen, neuron-specific enolase and cytokeratin fragment 21–1. The highest increasement of tumor marker sensitivity is up to 71.4%. The biosensing enhancement is attributed to the introduction of gold nanobumps on metasurfaces, which provides more hot-spot regions, higher localized near-field intensity and better optical impedance matching. Furthermore, the biosensing of HR metasurfaces effectively covers the threshold values of tumor markers for early lung cancer diagnosis, and is used for the detection of clinical serum samples. The testing deviation is less than 4% compared with commercial immunoassay, which implies promising applications on medical examinations. Our research provides a scientific guide to surface roughness engineering for plasmonic metasensing in the future point-of-care testing.

Plasmon-Enhanced Characterization of Single Extracellular Vesicles.

Extracellular vesicles (EVs) represent heterogeneous populations of membrane-bound vesicles shed from almost all kinds of cells. Although superior to conventional methods, most newly developed EV sensing platforms still require a certain number of EVs, measuring bulk signals from a group of vesicles. A new analytical approach that enables single EV analysis could be extremely valuable for understanding EVs' subtypes, heterogeneity, and production dynamics during disease development and progression. Here, we describe a new nanoplasmonic sensing platform for sensitive single EV analysis. Termed nPLEX-FL (nano-plasmonic EV analysis with enhanced fluorescence detection), the system amplifies EVs' fluorescence signals using periodic gold nanohole structures, enabling sensitive, multiplexed analysis of single EVs.

Dielectrophoretic trapping of nanosized biomolecules on plasmonic nanohole arrays for biosensor applications: simple fabrication and visible-region detection.

Surface plasmon resonance is an optical phenomenon that can be applied for label-free, real-time sensing to directly measure biomolecular interactions and detect biomarkers in solutions. Previous studies using plasmonic nanohole arrays have monitored and detected various biomolecules owing to the propagating surface plasmon polaritons (SPPs). Extraordinary optical transmission (EOT) that occurs in the near-infrared (NIR) and infrared (IR) regions is usually used for detection. Although these plasmonic nanohole arrays improve the sensitivity and throughput for biomolecular detection, these arrays have the following disadvantages: (1) molecular diffusion in the solution (making the detection of biomolecules difficult), (2) the device fabrication's complexities, and (3) expensive equipments for detection in the NIR or IR regions. Therefore, there is a need to fabricate plasmonic nanohole arrays as biomolecular detection platforms using a simple and highly reproducible procedure based on other SPP modes in the visible region instead of the EOT in the NIR or IR regions while suppressing molecular diffusion in the solution. In this paper, we propose the combination of a polymer-based gold nanohole array (Au NHA) obtained through an easy process as a simple platform and dielectrophoresis (DEP) as a biomolecule manipulation method. This approach was experimentally demonstrated using SPP and LSPR modes (not EOT) in the visible region and simple, label-free, rapid, cost-effective trapping and enrichment of nanoparticles (trapping time: <50 s) and bovine serum albumin (trapping time: <1000 s) was realized. These results prove that the Au NHA-based DEP devices have great potential for real-time digital and Raman bioimaging, in addition to biomarker detection.

Voltage-modulated surface plasmon resonance biosensors integrated with gold nanohole arrays.

Surface plasmon resonance (SPR) has emerged as one of the most efficient and attractive techniques for optical sensors in biological applications. The traditional approach of an EC (electrochemical)-SPR biosensor to generate SPR is by adopting a prism underneath the sensing substrate, and an angular scan is performed to characterize the reflectivity of target analytes. In this paper, we designed and investigated a novel optical biosensor based on a hybrid plasmonic and electrochemical phenomenon. The SPR was generated from a thin layer of gold nanohole array on a glass substrate. Using C-Reactive Protein (CRP) as the target analyte, we tested our device for different concentrations and observed the optical response under various voltage bias conditions. We observed that SPR response is concentration-dependent and can be modulated by varying DC voltages or AC bias frequencies. For CRP concentrations ranging from 1 to 1000 µg/mL, at the applied voltage of -600 mV, we obtained a limit of detection for this device of 16.5 ng/mL at the resonance peak wavelength of 690 nm. The phenomenon is due to spatial re-distribution of electron concentration at the metal-solution interface. The results suggest that CRP concentration can be determined from the SPR peak wavelength shift by scanning the voltages. The proposed new sensor structure is permissible for various future optoelectronic integration for plasmonic and electrochemical sensing.

Plasmonic Biosensing for Label-Free Detection of Two Hallmarks of Cancer Cells: Cell-Matrix Interaction and Cell Division.

Two key features of cancer cells are sustained proliferation and invasion, which is preceded by a modification of the adhesion properties to the extracellular matrix. Currently, fluorescence-based techniques are mainly used to detect these processes, including flow cytometry and fluorescence resonance energy transfer (FRET) microscopy. We have previously described a simple, fast and label-free method based on a gold nanohole array biosensor to detect the spectral response of single cells, which is highly dependent on the actin cortex. Here we used this biosensor to study two cellular processes where configuration of the actin cortex plays an essential role: cell cycle and cell–matrix adhesion. Colorectal cancer cells were maintained in culture under different conditions to obtain cells stopped either in G0/G1 (resting cells/cells at the initial steps of cell growth) or G2 (cells undergoing division) phases of the cell cycle. Data from the nanohole array biosensor showed an ability to discriminate between both cell populations. Additionally, cancer cells were monitored with the biosensor during the first 60 min after cells were deposited onto a biosensor coated with fibronectin, an extracellular matrix protein. Spectral changes were detected in the first 20 min and increased over time as the cell–biosensor contact surface increased. Our data show that the nanohole array biosensor provides a label-free and real-time procedure to detect cells undergoing division or changes in cell–matrix interaction in both clinical and research settings.

Refractive Index Biosensor Using Metamaterial Perfect Absorber Based on Graphene in Near-Infrared for Disease Diagnosis

This paper presents a metamaterial perfect absorber as a biosensor in the near-infrared region for biomedical molecular detection, such as urine concentration, malaria infection, bacillus bacteria, and cancer cell detection. In the proposed biosensor, an Au layer with a bracket-shaped cavity is utilized to boost electric field enhancement intensity in the vicinity of the nanohole. According to the capacitance of the bracket-shaped nanohole, changing the length of the hole controls the resonance wavelength. Due to the significant confinement of the electromagnetic field in the sharp edges and gaps, which excites Localized Surface Plasmon Resonances (LSPRs) in the metal-dielectric interface, near-unity absorption is obtained. Through evaluating the optical responses of the structure, via the finite element method (FEM), for different biomedical samples, high sensitivity of 2120.86 nm/RIU is acquired. In order to increase the sensitivity of the biosensor, a graphene layer is added between the dielectric layer and the gold nanohole layer. Adding graphene increases the LSPRs excitation and losses which yields a maximum sensitivity of 2500 nm/RIU. The presented biosensor with high sensitivity and compact size is a good candidate for biomedical purposes.

Wavelength-tunable dual-band edge plasmon mode based on gold edge-hole plasmonic nanostructure

Metal nanostructures have attracted attention because of their unique optical characteristics derived from localized surface plasmon resonance. In this study, gold nanoholes with edge structures were designed and characterized to possess two plasmon bands at different wavelengths. These bands were assigned to the plasmon modes that generated a concentrated electric field at the tip of the individual edge structures. Furthermore, wavelengths of these bands were independently tuned from the visible to near-infrared wavelengths with shape and size of the gold nanoholes and edge structures as variables. To demonstrate wavelength tuning, a gold nanostructure with edge plasmon bands at wavelengths of approximately 785 and 1064 nm (typical laser wavelengths for surface-enhanced Raman scattering and optical tweezers, respectively) was successfully obtained via optical simulation. The results indicate that the structure designed in this study provides a guideline for the design of optical devices with efficient multiple optical functions.

Rayleigh anomaly-enabled mode hybridization in gold nanohole arrays by scalable colloidal lithography for highly-sensitive biosensing

Abstract Plasmonic sensors exhibit tremendous potential to accomplish real-time, label-free, and high-sensitivity biosensing. Gold nanohole array (GNA) is one of the classic plasmonic nanostructures that can be readily fabricated and integrated into microfluidic platforms for a variety of applications. Even though GNA has been widely studied, new phenomena and applications are still emerging continuously expanding its capabilities. In this article, we demonstrated narrow-band high-order resonances enabled by Rayleigh anomaly in the nanohole arrays that are fabricated by scalable colloidal lithography. We fabricated large-area GNAs with different hole diameters, and investigated their transmission characteristics both numerically and experimentally. We showed that mode hybridization between the plasmon mode of the nanoholes and Rayleigh anomaly of the array could give rise to high-quality decapole resonance with a unique nearfield profile. We experimentally achieved a refractive index sensitivity, i.e., RIS up to 407 nm/RIU. More importantly, we introduced a spectrometer-free refractive index sensing based on lens-free smartphone imaging of GNAs with (intensity) sensitivity up to 137%/RIU. Using this platform, we realized the label-free detection of BSA molecules with concentration as low as 10−8 M. We believe our work could pave the way for highly sensitive and compact point-of-care devices with cost-effective and high-throughput plasmonic chips.