Plasmonic Nanopillars Research Articles

Wafer-Level Highly Dense Metallic Nanopillar-Enabled High-Performance SERS Substrates for Molecular Detection.

Seeking sensitive, large-scale, and low-cost substrates is highly important for practical applications of surface-enhanced Raman scattering (SERS) technology. Noble metallic plasmonic nanostructures with dense hot spots are considered an effective construction to enable sensitive, uniform, and stable SERS performance and thus have attracted wide attention in recent years. In this work, we reported a simple fabrication method to achieve wafer-scale ultradense tilted and staggered plasmonic metallic nanopillars filled with numerous nanogaps (hot spots). By adjusting the etching time of the PMMA (polymethyl methacrylate) layer, the optimal SERS substrate with the densest metallic nanopillars was obtained, which possessed a detection limit down to 10-13 M by using crystal violet as the detected molecules and exhibited excellent reproducibility and long-term stability. Furthermore, the proposed fabrication approach was further used to prepare flexible substrates; for example, a SERS flexible substrate was proven to be an ideal platform for analyzing low-concentration pesticide residues on curved fruit surfaces with significantly enhanced sensitivity. This type of SERS substrate possesses potential in real-life applications as low-cost and high-performance sensors.

Plasmonic Nanopillars-A Brief Investigation of Fabrication Techniques and Biological Applications.

Nanopillars (NPs) are submicron-sized pillars composed of dielectrics, semiconductors, or metals. They have been employed to develop advanced optical components such as solar cells, light-emitting diodes, and biophotonic devices. To integrate localized surface plasmon resonance (LSPR) with NPs, plasmonic NPs consisting of dielectric nanoscale pillars with metal capping have been developed and used for plasmonic optical sensing and imaging applications. In this study, we studied plasmonic NPs in terms of their fabrication techniques and applications in biophotonics. We briefly described three methods for fabricating NPs, namely etching, nanoimprinting, and growing NPs on a substrate. Furthermore, we explored the role of metal capping in plasmonic enhancement. Then, we presented the biophotonic applications of high-sensitivity LSPR sensors, enhanced Raman spectroscopy, and high-resolution plasmonic optical imaging. After exploring plasmonic NPs, we determined that they had sufficient potential for advanced biophotonic instruments and biomedical applications.

Enhanced Optical Response in Au Nanopillar/La0.67Sr0.33MnO3 Film Composites: Implications for Magnetooptical Devices

Metal oxide vertically aligned nanocomposite thin films have been of considerable interest for hot-carrier-based light harvesting and active plasmonic applications. Herein, we present femtosecond pump–probe spectroscopy studies on a nanocomposite thin film with plasmonic Au nanopillars vertically aligned in a ferromagnetic La0.67Sr0.33MnO3 (LSMO) matrix. Our measurements reveal that the carrier decay of Au/LSMO films qualitatively follows that of pure LSMO with a two-component relaxation. In the presence of Au nanopillars, the charge generation within the LSMO film is enhanced by a factor of ∼40, and the spin–lattice relaxation time associated with demagnetization is substantially decreased from 259.6 to 7.7 ps. The enhanced nonequilibrium dynamics and energy transfer between the lattice and spin system in the Au/LSMO films can be well modeled using an extended three-temperature model. These Au/LSMO thin films can be potentially useful in ultrafast photoelectric and magnetooptical applications.

Organometallic hotspot engineering for ultrasensitive EC-SERS detection of pathogenic bacteria-derived DNAs

The sensitivity and limit-of-detection (LOD) of the traditional surface-enhanced Raman spectroscopy (SERS) platform suffer from the requirement of precise positioning of small analytes, including DNAs and bacteria, into narrow hotspots. In this study, a novel SERS sensor was developed using electrochemical deposition onto metal nanopillars (ECOMPs) combined with complementary DNAs (cDNAs) for the detection of pathogenic bacteria. Applying a redox potential to AuCl4− ions actively engineered the organometallic hotspots based on the cDNAs in a short time (<10 min) and simultaneously produced SERS signals. Because of the influence of potential-driven morphological properties on the SERS efficiency in the cDNA domains and the resonant coupling of internal fields with the fields confined between adjacent ECOMPs-cDNAs, the optimum growth time was determined to be 5 min. The EC-SERS detection and discrimination of Enterococcus faecium and Staphylococcus aureus were successfully carried out because of the DNA complementarity. Compared with plasmonic metal nanopillars (MPs)-cDNAs, the enhancement factor of the ECOMPs-cDNAs was estimated to be ∼2.0 × 103. A quantitative investigation revealed that a highly linear progression in the target DNA concentration range (0.05–100 nM) and a LOD of ∼0.035 nM were achieved. The specificity of the ECOMPs-cDNAs was validated by cross-hybridization. The platform was also used to assay human whole blood containing 0.1 nM bacterial DNAs. The proposed strategy provides the potential for highly sensitive SERS-based multiplex DNA detection in clinical diagnostics.

Ultra-unidirectional Emission with Enhanced Spectral Splitting Based on Plasmonic Nano-pillars and its Metasurface

Ultra-unidirectional Emission with Enhanced Spectral Splitting Based on Plasmonic Nano-pillars and its Metasurface

Enhanced SPR-Based Localized and Bulk Sensing Using a Plasmonic Nanopillar Array With Spacer

We report a substantially improved localized and bulk sensing response of a plasmonic sensor based on a plasmonic nanopillar array spacer-separated from a plasmonic thin film and operated using the conventional Kretschmann configuration. This paper describes theoretical investigations of the spectral and angular interrogation of the proposed sensors to determine the spectral or angular reflectivity minima. Shifts in the reflectivity minima are determined to obtain information on perturbations in localized (local binding analyte layer sensing) and bulk refractive index (bulk medium sensing) on the sensor surface. Optimization of the structural parameters of the proposed sensor yields a highly enhanced sensor performance, with an extremely high sensitivity (9920 nm RIU^&#x2212;1) and figure of merit (58.2 RIU^&#x2212;1) for bulk sensing response, as well as extremely high sensitivity (76 nm/nm) and figure of merit (0.5 nm^&#x2212;1) for localized sensing response upon spectral interrogation of the sensor. The localized surface sensitivity for the proposed sensor, which is evaluated to be 76 nm/nm, is higher than what has been reported till now. The proposed sensors do not require any sophisticated optical set-ups and can be implemented on the optical setups used for the conventional Kretschmann configuration based sensors. The proposed sensor design could easily be fabricated using the state-of-the-art top-down nanofabrication approaches and could be employed for developing highly sensitive biosensing platforms.

Exploring near-field sensing efficiency of complementary plasmonic metasurfaces for immunodetection of tumor markers

Plasmonic metasurface biosensors have great potential on label-free high-throughput clinical detection of human tumor markers. In the past decades, nanopillar and nanohole metasurfaces have become the common choices for plasmonic biosensing, because they typically enable universal simple large-area nanopatterns via a low-cost reproducible fabrication manner. The two kinds of metasurfaces have the complementary shapes and are used to be assumed as the same type of two-dimensional plasmonic nanograting for biosensing. Up to date, there is still a lack of comparison study on their biosensing performance, which is critical to guide their better applications on tumor marker detection. In this study, we compare the bulk/surface refractive index and sensitivity of plasmonic nanopillar (PNP) and plasmonic nanohole (PNH) metasurfaces in order to evaluate their biosensing capabilities. The sensing physics about their space near-field utilization is systematically revealed. The PNH metasurface demonstrates a higher biomolecule sensitivity versus the complementary PNP metasurface, and its limit of detection for bovine serum albumin reaches ∼0.078 ng/mL, which implies a greater potential of detecting cancer biomarkers. We further adopt the PNH metasurfaces for immunoassay of three typical tumor markers by testing clinical human serum samples. The results imply that the immunodetection of alpha-fetoprotein has the most optimal sensing efficiency with the lowest detection concentration (<5 IU/mL), which is much lower than its clinical diagnosis threshold of ∼16.5 IU/mL for medical examination. Our work has not only illuminated the distinct biosensing properties of complementary metasurfaces, but also provided a promising way to boost plasmonic biosensing for point-of-care testing.

Multifunctional Metal-Oxide Nanocomposite Thin Film with Plasmonic Au Nanopillars Embedded in Magnetic La0.67Sr0.33MnO3 Matrix.

Searching for multifunctional materials with tunable magnetic and optical properties has been a critical task toward the implementation of future integrated optical devices. Vertically aligned nanocomposite (VAN) thin films provide a unique platform for multifunctional material designs. Here, a new metal-oxide VAN has been designed with plasmonic Au nanopillars embedded in a ferromagnetic La0.67Sr0.33MnO3 (LSMO) matrix. Such Au-LSMO nanocomposite presents intriguing plasmon resonance in the visible range and magnetic anisotropy property, which are functionalized by the Au and LSMO phase, respectively. Furthermore, the vertically aligned nanostructure of metal and dielectric oxide results in the hyperbolic property for near-field electromagnetic wave manipulation. Such optical and magnetic response could be further tailored by tuning the composition of Au and LSMO phases.

A wafer-scale fabrication method for three-dimensional plasmonic hollow nanopillars.

Access to nanofabrication strategies for crafting three-dimensional plasmonic structures is limited. In this work, a fabrication strategy to produce 3D plasmonic hollow nanopillars (HNPs) using Talbot lithography and I-line photolithography is introduced. This method is named subtractive hybrid lithography (SHL), and permits intermixed usage of nano-and-macroscale patterns. Sputter-redeposition of gold (Au) on the SHL resist pattern yields large areas of dense periodic Au-HNPs. These Au-HNPs are arranged in a square unit cell with a 250 nm pitch. The carefully controlled fabrication process resulted in Au-HNPs with nanoscale dimensions over the Au-HNP dimensions such as an 80 ± 2 nm thick solid base with a 133 ± 4 nm diameter, and a 170 ± 10 nm high nano-rim with a 14 ± 3 nm sidewall rim-thickness. The plasmonic optical response is assessed with FDTD-modeling and reveals that the highest field enhancement is at the top of the hollow nanopillar rim. The modeled field enhancement factor (EF) is compared to the experimental analytical field enhancement factor, which shows to pair up with ca. 103 < EF < 104 and ca. 103 < EF < 105 for excitation wavelengths of 633 and 785 nm. From a broader perspective, our results can stimulate the use of Au-HNPs in the fields of plasmonic sensors and spectroscopy.

High-throughput fabrication of high aspect ratio Ag/Al nanopillars for optical detection of biomarkers.

Nanomaterial-based optical techniques for biomarker detection have garnered tremendous attention from the nanofabrication community due to their high precision and enhanced limit of detection (LoD) features. These nanomaterials are highly responsive to local refractive index (RI) fluctuations, and their RI unit sensitivity can be tuned by varying the chemical composition, geometry, and dimensions of the utilized nanostructures. To improve the sensitivity and LoD values of these nanomaterials, it is common to increase both dimensions and aspect ratios of the fabricated nanostructures. However, limited by the complexity, prolonged duration, and elevated costs of the available nanofabrication techniques, mass production of these nanostructures remains challenging. To address not only high accuracy, but also speed and production effectiveness in these nanostructures' fabrication, our work reports, for the first time, a fast, high-throughput, and cost-effective nanofabrication protocol for routine manufacturing of polymer-based nanostructures with high sensitivity and calculated LoD in the pM range by utilizing anodized aluminum oxide (AAO) membranes as templates. Specifically, our developed platform consists of arrays of nearly uniform polystyrene nanopillars with an average diameter of ∼185 nm and aspect ratio of ∼11. We demonstrate that these nanostructures can be produced at a high speed and a notably low price, and that they can be efficiently applied for biosensing purposes after being coated with aluminum-doped silver (Ag/Al) thin films. Our platform successfully detected very low concentrations of human C-reactive protein (hCRP) and SARS-CoV-2 spike protein biomarkers in human plasma samples with LoDs of 11 and 5 pM, respectively. These results open new opportunities for day-to-day fabrication of high aspect ratio arrays of nanopillars that can be used as a base for nanoplasmonic sensors with competitive LoD values. This, in turn, contributes to the development of point-of-care devices and further improvement of the existing nanofabrication techniques, thereby enriching the fields of pharmacology, clinical analysis, and diagnostics.

The use of anodized alumina molds for the fabrication of polymer nanopillar arrays as SERS substrates with tunable properties

Due to the increasing interest for the sensitive detection of molecules in various scientific fields, surface-enhanced Raman spectroscopy (SERS) arises as a powerful technique that can provide single molecule sensing capability as well as fingerprint specificity. In order to obtain highly enhanced and reproducible Raman signals for such purposes, fabrication of periodically engineered nanostructures with projected hotspot formation is intensively studied. Herein, we report a non-lithographic method for fabricating periodic arrays of plasmonic nanopillars displaying tunable spectral features by employing nanoporous anodic alumina molds (AAMs). AAMs with ˜80 nm and ˜100 nm pore sizes were used to fabricate drop-casted polycarbonate films possessing small nanopillar arrays (SNPC) and large nanopillar arrays (LNPC), respectively. These films were then modified with a facile polydopamine (PDA)-assisted Ag coating step. The SERS spectra of the resultant Ag@SNPC and Ag@LNPC platforms indicate that both the mold topography as well as the coating period has a direct influence on the enhancement of the Raman signals of a model reporter dye. The Ag@LNPC platforms always displayed intensified SERS signals compared to Ag@SNPC counterparts, and this trend was confirmed with simulation studies. The intensity difference was attributed to improved probability of hotspot formation for the more closely arranged nanoantennas on the Ag@LNPC platform. Both substrates showed enhanced SERS signals compared to Ag deposited flat PC substrates and reproducible signals with relative standard deviation values ˜10% were obtained from independently prepared samples.

Highly Sensitive and Selective Nanogap-Enhanced SERS Sensing Platform.

This paper reports a highly sensitive and selective surface-enhanced Raman spectroscopy (SERS) sensing platform. We used a simple fabrication method to generate plasmonic hotspots through a direct maskless plasma etching of a polymer surface and the surface tension-driven assembly of high aspect ratio Ag/polymer nanopillars. These collapsed plasmonic nanopillars produced an enhanced near-field interaction via coupled localized surface plasmon resonance. The high density of the small nanogaps yielded a high plasmonic detection performance, with an average SERS enhancement factor of 1.5 × 107. More importantly, we demonstrated that the encapsulation of plasmonic nanostructures within nanofiltration membranes allowed the selective filtration of small molecules based on the degree of membrane swelling in organic solvents and molecular size. Nanofiltration membrane-encapsulated SERS substrates do not require pretreatments. Therefore, they provide a simple and fast detection of toxic molecules using portable Raman spectroscopy.

Raman Scattering Mapping: Sensitive and Reproducible Immunoassay of Multiple Mycotoxins Using Surface‐Enhanced Raman Scattering Mapping on 3D Plasmonic Nanopillar Arrays (Small 39/2018)

Raman Scattering Mapping: Sensitive and Reproducible Immunoassay of Multiple Mycotoxins Using Surface‐Enhanced Raman Scattering Mapping on 3D Plasmonic Nanopillar Arrays (Small 39/2018)

Radiative Enhancement of Single Quantum Emitters in WSe2 Monolayers Using Site-Controlled Metallic Nanopillars

Plasmonic nano-structures provides an efficient way to control and enhance the radiative properties of quantum emitters. Coupling these structures to single defects in low-dimensional materials provides a particularly promising material platform to study emitter-plasmon interactions because these emitters are not embedded in a surrounding dielectric. They can therefore approach a near-field plasmonic mode to nanoscale distances, potentially enabling strong light-matter interactions. However, this coupling requires precise alignment of the emitters to the plasmonic mode of the structures, which is particularly difficult to achieve in a site-controlled structure. We present a technique to generate quantum emitters in 2D tungsten diselenide (WSe2) coupled to site-controlled plasmonic nano-pillars. The plasmonic nano-pillars induce strain in the two dimensional material which generates quantum emitters near the high-field region of the plasmonic mode. The electric field of the nano-pillar mode lies close to parallel with the two-dimensional material, and is therefore in the correct orientation to couple to quantum emitters. Interactions between the emitter and plasmonic mode result in an enhanced spontaneous emission and increased brightness. This approach may enable bright site-controlled non-classical light sources for applications in quantum communication and optical quantum computing.

Sensitive and Reproducible Immunoassay of Multiple Mycotoxins Using Surface-Enhanced Raman Scattering Mapping on 3D Plasmonic Nanopillar Arrays.

A surface-enhanced Raman scattering-based mapping technique is reported for the highly sensitive and reproducible analysis of multiple mycotoxins. Raman images of three mycotoxins, ochratoxin A (OTA), fumonisin B (FUMB), and aflatoxin B1 (AFB1) are obtained by rapidly scanning the surface-enhanced Raman scattering (SERS) nanotags-anchoring mycotoxins captured on a nanopillar plasmonic substrate. In this system, the decreased gap distance between nanopillars by their leaning effects as well as the multiple hot spots between SERS nanotags and nanopillars greatly enhances the coupling of local plasmonic fields. This strong enhancement effect makes it possible to perform a highly sensitive detection of multiple mycotoxins. In addition, the high uniformity of the densely packed nanopillar substrate minimizes the spot-to-spot fluctuations of the Raman peak intensity in the scanned area when Raman mapping is performed. Consequently, this makes it possible to gain a highly reproducible quantitative analysis of mycotoxins. The limit of detections (LODs) are determined to be 5.09, 5.11, and 6.07 pg mL-1 for OTA, FUMB, and AFB1, and these values are approximately two orders of magnitude more sensitive than those determined by the enzyme-linked immunosorbent assays. It is believed that this SERS-based mapping technique provides a facile tool for the sensitive and reproducible quantification of various biotarget molecules.

Culture-Free Detection of Bacterial Pathogens on Plasmonic Nanopillar Arrays Using Rapid Raman Mapping.

We utilized a fast Raman spectral mapping technique for fast detection of bacterial pathogens. Three-dimensional (3D) plasmonic nanopillar arrays were fabricated using the nanolithography-free process consisting of maskless Ar plasma treatment of a polyethylene terephthalate substrate and subsequent metal deposition. Bacterial pathogens were immobilized on the positively charged poly(l-lysine)-coated 3D plasmonic substrate through electrostatic interactions. Then, the bacterial surfaces were selectively labeled with antibody-conjugated surface-enhanced Raman scattering (SERS) nanotags, and Raman mapping images were collected and statistically analyzed for quantitative analysis of bacteria. Salmonella typhimurium was selected as a model pathogen bacterium to confirm the efficacy of our SERS imaging technique. Minimum number of Raman mapping points with statistical reliability was determined to reduce assay time. It was possible to get a statistically reliable standard calibration curve for 529 pixels (laser spot with 60 μm interval), which required a total mapping time of 45 min to get a standard calibration curve for five different concentrations of bacteria in the 0 to 106 CFU/mL range. No amplification step was necessary for quantification because low-abundance target bacteria could be measured using the Raman spectral mapping technique. Therefore, this approach allows accurate quantification of bacterial pathogens without any culturing or enrichment process.

Surface Energy‐Controlled SERS Substrates for Molecular Concentration at Plasmonic Nanogaps

AbstractPositioning probe molecules at electromagnetic hot spots with nanometer precision is required to achieve highly sensitive and reproducible surface‐enhanced Raman spectroscopy (SERS) analysis. In this article, molecular positioning at plasmonic nanogaps is reported using a high aspect ratio (HAR) plasmonic nanopillar array with a controlled surface energy. A large‐area HAR plasmonic nanopillar array is generated using a nanolithography‐free simple process involving Ar plasma treatment applied to a smooth polymer surface and the subsequent evaporation of metal onto the polymer nanopillars. The surface energy can be precisely controlled through the selective removal of an adsorbed self‐assembled monolayer of low surface‐energy molecules prepared on the plasmonic nanopillars. This process can be used to tune the surface energy and provide a superhydrophobic surface with a water contact angle of 165.8° on the one hand or a hydrophilic surface with a water contact angle of 40.0° on the other. The highly tunable surface wettability is employed to systematically investigate the effects of the surface energy on the capillary‐force‐induced clustering among the HAR plasmonic nanopillars as well as on molecular concentration at the collapsed nanogaps present at the tops of the clustered nanopillars.

A high-performance and low cost SERS substrate of plasmonic nanopillars on plastic film fabricated by nanoimprint lithography with AAO template

As a powerful spectroscopy technique, surface-enhanced Raman scattering (SERS) can provide non-destructive and sensitive characterization down to a single molecular level. Aiming to the main challenges of high-performance SERS-active substrates for their real-world applications involving the ultra-sensitive and reproducible signals detection and signal uniformity with large-area, herein, a facile and reliable strategy based on combination of thermal imprinting polycarbonate (PC) film with porous anodic aluminum oxide (AAO) mold and E-beam evaporation of gold is provided to fabricate a high-quality SERS-active substrate consisting of ultra-dense hot-spots with large-area uniformity. Two kinds of sub-10 nm gaps were obtained, including the nanogaps between the neighboring gold coated PC-nanopillars and those between gold on the top of the nanopillars and that on the base, which actually build up a three-dimensional (3D) hot-spot network for high-performance SERS detection. The effect of structural parameters on SERS enhancement was investigated numerically and experimentally, and by optimizing the structural parameters, a remarkable average SERS enhancement factor up to of 1.4×108 is achieved and it shows an excellent reproducibility with a relative standard deviation of 18%, which allows for enhanced practicability in the application of quantitative biochemical detection.

Tapered fiber nanoprobes: plasmonic nanopillars on tapered optical fiber tips for large EM enhancement.

Employing finite difference time domain simulations, we demonstrate that electromagnetic field enhancement is substantially greater for tapered optical fibers with plasmonic nanostructures present on their tips as compared with non-tapered optical fibers having those plasmonic nanostructures, or with tapered optical fibers without the plasmonic nanostructures. We also carried out fabrication of plasmonic nanostructures on optical fiber tips.

Optical properties of plasmonic nanopillars in extended quasi-static limits

An extended method based on the long-wavelength approximations is introduced to investigate the optical properties of finite-size metal nanopillars for different incident light polarizations. In this proposed method, the optical depolarization factors are the key parameters and strongly depend on the position of the considered point dipole inside the irregular-shaped nanoparticles. Interestingly, depending on the polarization, it is shown that the conventional point dipole positioned at the center of a nonspherical nanoparticle seldom is the proper choice as its simple electromagnetic model. The adequate off-center point, though, is determined and physically associated with the electric-field distribution inside the nanoparticle, which is supported by numerical computations. Remarkably, the proposed extended MLWA could extend the quasi-static limits and, consequently, more accurately predict the optical properties of the finite-size plasmonic nanopillar.