3D Surface-enhanced Raman Scattering Substrates Research Articles

3D Surface-Enhanced Raman Scattering Substrate Based on an Array of Self-Assembled Au@SiO2 Microspheres

A quasi-periodic array of 3D gold-nanoparticle-capped SiO2 microspheres (Au@SiO2) was designed and prepared with a facile approach to enhance the Raman signal intensity of adsorbed biomolecules. Through adjusting the thickness and annealing of Au thin films initially deposited on arrays of self-assembled SiO2 microspheres, we were able to control the diameter of Au nanoparticles and their interparticle spacing to produce two types of plasmonic near-field hot spots, locating at the gaps of such densely arranged Au nanoparticles on individual SiO2 microspheres and in the gap regions of neighboring SiO2 microspheres, respectively. Such double near-field enhancement mechanism leads to a surface-enhanced Raman scattering (SERS) enhancement factor up to 3 × 106 for Rhodamine 6G molecules. The SERS signal intensity was highly uniform with a relative standard deviation of 4.5%. This 3D SERS substrate has significant potential for various applications in the field of SERS detection of analytes and wearable biosensing.

Silver Dendrite‐Coated Silicon Pyramid Substrate as Surface‐Enhanced Raman Scattering Probe for Detecting Glucose

Raman spectroscopy offers a rapid and nondestructive method for qualitatively and quantitatively analyzing the molecular structure of substances. Herein, a facile and cost‐effective approach for the preparation of three‐dimensional (3D) surface‐enhanced Raman scattering (SERS) substrates is proposed, in which pyramid structures are fabricated using silicon anisotropic wet etching and silver dendrites are decorated on these silicon pyramid (PSi) substrates by immersing them in a mixture of hydrofluoric acid and silver nitrate for several minutes. The 3D SERS substrates, based on PSi coated with Ag dendrites, reveal high‐performance SERS enhancement (with an analytical enhancement factor reaching 3.54 × 1010) and can detect rhodamine 6G (R6G) in the presence of chemical enhancer (lithium chloride) at low concentrations down to 10−11 m. For glucose detection, 2‐thienylboronic acid is employed to faciliate glucose attachment to the substrate surface, achieving a detection limit as low as 10−6 m. The substrate exhibits good repeatability with a relative standard deviation of 11.223%, as well as reusability and long‐term stability for detection. The results also highlight the excellent sensitivity of the PSi‐based SERS substrate, which is expected to be instrumental in biochemical analysis and holds significant potential for developing noninvasive glucose sensor for diabetic patients using saliva samples.

Self-Assembled Three-Dimensional Polyamide/Silver Nanoparticle Pore Array as a Highly Sensitive and Reproducible SERS Substrate for Pesticide Detection in Water.

In this study, silver nanoparticles (AgNPs) are self-assembled onto the polyamide (PA) pore array through hydrogen bonding, resulting in and optimizing the PA/Ag 3D pore array substrates. The best surface-enhanced Raman scattering (SERS) substrate is obtained with a pore depth of 500 nm in the PA array, 30 nm AgNPs, at a pH of 5.0, and a 24 h assembly time. The SERS performance of the substrates is assessed using rhodamine 6G (R6G) as a probe molecule. The detection limit of the R6G molecule reaches 10-13 M, and the relative standard deviation is under 20%, indicating good enhancement ability and reproducibility. Furthermore, label-free detection of pesticide contaminant diquat with a detection limit of 2.69 × 10-9 M is achieved using the optimized 3D substrate, which meets environmental monitoring requirements for drinking water. The findings demonstrate that this 3D SERS substrate has promising potential for use and development in the fields of contaminant detection and chemical sensing.

Mesoporous One-Component Gold Microshells as 3D SERS Substrates.

Surface-enhanced Raman scattering (SERS) is a powerful analytical tool for label-free analysis that has found a broad spectrum of applications in material, chemical, and biomedical sciences. In recent years, a great interest has been witnessed in the rational design of SERS substrates to amplify Raman signals and optionally allow for the selective detection of analytes, which is especially essential and challenging for biomedical applications. In this study, hard templating of noble metals is proposed as a novel approach for the design of one-component tailor-made SERS platforms. Porous Au microparticles were fabricated via dual ex situ adsorption of Au nanoparticles and in situ reduction of HAuCl4 on mesoporous sacrificial microcrystals of vaterite CaCO3. Elimination of the microcrystals at mild conditions resulted in the formation of stable mesoporous one-component Au microshells. SERS performance of the microshells at very low 0.4 µW laser power was probed using rhodamine B and bovine serum albumin showing enhancement factors of 2 × 108 and 8 × 108, respectively. The proposed strategy opens broad avenues for the design and scalable fabrication of one-component porous metal particles that can serve as superior SERS platforms possessing both excellent plasmonic properties and the possibility of selective inclusion of analyte molecules and/or SERS nanotags for highly specific SERS analysis.

Highly Sensitive and Reproducible SERS Substrates Based on Ordered Micropyramid Array and Silver Nanoparticles.

The construction of a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) substrate is the key factor that restricts its practical application. In this paper, a three-dimensional (3D) SERS substrate based on ordered micropyramid array and silver nanoparticles (MPA/AgNPs 3D-SERS) was constructed using the roll-to-plate embossing technology and a hydrothermal method, which provided an efficient and low-cost preparation process for the SERS substrate. Using rhodamine 6G (R6G) as a probe molecule, the performance of an MPA/AgNP 3D-SERS substrate was studied in detail, whose minimum detection limit was 10-12 M and the enhancement factor was calculated as 8.8 × 109, indicating its high sensitivity. In addition, the minimum relative standard deviation (RSD) for the MPA/AgNP 3D-SERS substrate was calculated as 4.99%, and SERS performance basically had no loss after 12 days of placement, which indicated that the prepared SERS substrate had excellent stability and repeatability. At last, the thiram detection application of the MPA/AgNP 3D-SERS substrate was also investigated. The results showed that the minimum detection limit was 1 × 10-7 M, and quantitative analysis of pesticide residues could be realized. This research could provide useful guidance for the efficient and low-cost fabrication of highly sensitive and reproducible SERS substrates.

Size‐Tunable Gold Aerogels: A Durable and Misfocus‐Tolerant 3D Substrate for Multiplex SERS Detection

AbstractThe research on surface‐enhanced Raman scattering (SERS) continuously draws wide attention because of its high detection sensitivity. However, the commonly investigated 2D SERS substrates cannot fully utilize the 3D active focal volume and require a tight focus on the correct plane, retarding signal enhancement and flexible use. Here, self‐supported gold aerogels of centimeter‐dimension with tunable ligament sizes are designed as 3D SERS substrates, featuring hot spots throughout the entire network. Unveiling a universal ligament‐size‐effect, the optimized gold aerogel showcases much larger enhancement factors compared to a 8 nm Au film toward dyes, pesticides, and carcinogens (up to 109). Aside from an excellent reusability and an exceptional stability (> 1 month), an outstanding misfocus tolerance (>300 µm along the z‐axis) is also demonstrated for such aerogel‐based SERS substrates for multiplex detection. This work may expand the application scope of metal aerogels and lay the foundation for designing next‐generation 3D SERS substrates.

Facile Microfluidic Fabrication of 3D Hydrogel SERS Substrate with High Reusability and Reproducibility via Programmable Maskless Flow Microlithography

AbstractIn the field of surface‐enhanced Raman scattering (SERS), advances in nanotechnology and surface chemistry have contributed to fabricating the metal substrates with highly sophisticated architectures and strong binding affinity to target molecules which enhanced the sensitivity to target molecules. However, the elaborate yet complicated steps for the synthesis, patterning, and surface modification of metal substrates have often resulted in compromising the reliability, reproducibility, and reusability as SERS substrates. Here, a fully programmable and automated digital maskless flow microlithography process that spatiotemporally controls the fluid flow, UV irradiation, and the shape and location of SERS polymer matrix is provided to fabricate a reliable, reproducible, and reusable hydrogel‐based 3D SERS substrate. The SERS substrates are located inside the microfluidic device in the form of disk‐shaped hydrogels. By rationally designing the functional group chemistry of the hydrogel microposts, Ag nanoparticles are homogeneously synthesized in situ, a target molecule is amplified by 25‐fold inside the microposts, and an enhancement factor as high as 2.4 × 108 is observed. Furthermore, a highly reusable multitarget sensing capability is demonstrated by a sequential analysis of multiple analytes without the trace of former analytes via the intermittent washing step.

A Paper-Fiber-Supported 3D SERS Substrate

Surface-enhanced Raman scattering (SERS) spectroscopy is an effective approach for trace-level detection of molecular substance. Plasmonic metallic nanostructures with high distribution densities and small gap widths are always expected for constructing SERS substrates. We report here a paper-based SERS substrate, where the three-dimensional (3D) network of paper fibers was used as the platform for supporting the gold nanoparticle clusters. Such a 3D arrangement of plasmonic porous clusters supplies high-density hotspots with large total volume and large surface area for the interaction with molecules. Comparison between different papers found that the filter papers commonly available in labs are the best choice. An enhancement factor higher than 104 has been achieved in the detection of R6G molecules. The preparation of such SERS substrates is very simple and convenient, implying low-cost, disposable, and environment-friendly SERS techniques. Furthermore, the paper-based flexible SERS substrates can be easily tailored into different shapes and sizes for fitting different applications.

Facile fabrication of Ag dendrite-integrated anodic aluminum oxide membrane as effective three-dimensional SERS substrate

A novel surface enhanced Raman scattering (SERS)-active substrate has been successfully developed, where Ag-dendrites are assembled on the surface and embedded in the channels of anodic aluminum oxide (AAO) membrane, via electrodeposition in AgNO3/PVP aqueous system. Reaction conditions were systematically investigated to attain the best Raman enhancement. The growth mechanism of Ag dendritic nanostructures has been proposed. The Ag dendrite-integrated AAO membrane with unique hierarchical structures exhibits high SERS activity for detecting rhodamine 6G with a detection limit as low as 1×10−11M. Furthermore, the three-dimensional (3D) substrates display a good reproducibility with the average intensity variations at the major Raman peak less than 12%. Most importantly, the 3D SERS substrates without any surface modification show an outstanding SERS response for the molecules with weak affinity for noble metal surfaces. The potential application for the detection of polycyclic aromatic hydrocarbons (PAHs) was evaluated with fluoranthene as Raman target molecule and a sensitive SERS detection with a limit down to 10−8M was reached. The 3D SERS-active substrate shows promising potential for rapid detection of trace organic pollutants even weak affinity molecules in the environment.

Ag Nanoparticles Decorated Cactus-Like Ag Dendrites/Si Nanoneedles as Highly Efficient 3D Surface-Enhanced Raman Scattering Substrates toward Sensitive Sensing

Surface-enhanced Raman scattering (SERS) has been considered as a promising sensing technique to detect low-level analytes. However, its practical application was hindered owing to the lack of uniform SERS substrates for ultrasensitive and reproducible assay. Herein, inspired by the natural cactus structure, we developed a cactus-like 3D nanostructure with uniform and high-density hotspots for highly efficient SERS sensing by both grafting the silicon nanoneedles onto Ag dendrites and subsequent decoration with Ag nanoparticles. The hierarchical scaffolds and high-density hotspots throughout the whole substrate result in great amplification of SERS signal. A high Raman enhancement factor of crystal violet up to 6.6 × 10(7) was achieved. Using malachite green (MG) as a model target, the fabricated SERS substrates exhibited good reproducibility (RSD ∼ 9.3%) and pushed the detection limit down to 10(-13) M with a wide linear range of 10(-12) M to 10(-7) M. Excellent selectivity was also demonstrated by facilely distinguishing MG from its derivative, some organics, and coexistent metal ions. Finally, the practicality and reliability of the 3D SERS substrates were confirmed by the quantitative analysis of spiked MG in environmental water with high recoveries (91.2% to 109.6%). By virtue of the excellent performance (good reproducibility, high sensitivity, and selectivity), the cactus-like 3D SERS substrate has great potential to become a versatile sensing platform in environmental monitoring, food safety, and medical diagnostics.

Obviously Angular, Cuboid-Shaped TiO2 Nanowire Arrays Decorated with Ag Nanoparticle as Ultrasensitive 3D Surface-Enhanced Raman Scattering Substrates

In recent years, surface-enhanced Raman scattering (SERS) has received renewed attention, because of its nondestructive, ultrasensitive, and rapid analysis, detection, and imaging. Development of SERS substrates with high sensitivity and excellent stability is of great importance to realize its practical applications in trace analysis, bio diagnosis, and in vivo studies. In this work, we demonstrate wafer-scale Ag-nanoparticle-decorated, obviously angular, quasi-vertically aligned cuboid-shaped TiO2 nanowire arrays (TiO2-NWs), as ultrasensitive and uniform 3D SERS substrates. A detection limit of 10–15 M rhodamine 6G molecules and an analytical enhancement factor of 1012 were achieved on the cuboid-shaped TiO2-NWs arrays with 9 min Ag-sputtering. This is the best result obtained among the literature values on Ag-modified semiconductor SERS substrates. More importantly, the optimized TiO2-Ag also exhibits excellent stability and uniformity. The excellent SERS performance is attributed to the “cusp” and “ga...