Surface‐Enhanced Raman Scattering Using Microstructured Optical Fiber Substrates

Microstructured optical fibers (MOFs) represent a promising platform technology for fully integrated next generation surface enhanced Raman scattering (SERS) sensors and plasmonic devices. In this paper we demonstrate silver nanoparticle substrates for SERS detection within MOF templates with exceptional temporal and mechanical stability, using organometallic precursors and a high‐pressure chemical deposition technique. These 3D substrates offer significant benefits over conventional planar detection geometries, with the long electromagnetic interaction lengths of the optical guided fiber modes exciting multiple plasmon resonances along the fiber. The large Raman response detected when analyte molecules are infiltrated within the structures can be directly related to the deposition profile of the nanoparticles within the MOFs via electrical characterization.     

Fabrication of a Macroporous Microwell Array for Surface‐Enhanced Raman Scattering

Here, a colloidal templating procedure for generating high‐density arrays of gold macroporous microwells, which act as discrete sites for surface‐enhanced Raman scattering (SERS), is reported. Development of such a novel array with discrete macroporous sites requires multiple fabrication steps. First, selective wet‐chemical etching of the distal face of a coherent optical fiber bundle produces a microwell array. The microwells are then selectively filled with a macroporous structure by electroless template synthesis using self‐assembled nanospheres. The fabricated arrays are structured at both the micrometer and nanometer scale on etched imaging bundles. Confocal Raman microscopy is used to detect a benzenethiol monolayer adsorbed on the macroporous gold and to map the spatial distribution of the SERS signal. The Raman enhancement factor of the modified wells is investigated and an average enhancement factor of 4 × 10⁴ is measured. This demonstrates that such nanostructured wells can enhance the local electromagnetic field and lead to a platform of ordered SERS‐active micrometer‐sized spots defined by the initial shape of the etched optical fibers. Since the fabrication steps keep the initial architecture of the optical fiber bundle, such ordered SERS‐active platforms fabricated onto an imaging waveguide open new applications in remote SERS imaging, plasmonic devices, and integrated electro‐optical sensor arrays.     

Highly Reproducible Surface‐Enhanced Raman Scattering on a Capillarity‐Assisted Gold Nanoparticle Assembly

A facile method based on capillarity‐assisted assembly is used to fabricate high‐performance surface‐enhanced Raman scattering (SERS) substrates employing clean Au nanoparticles (NPs). This method is better than micro‐channel way because the former may supply large‐area uniform assembly and overcome the uneven radial distribution. Such densely‐arranged assembly of Au NPs exhibits high reproducibility and large Raman enhancement factors of 3 × 10¹⁰, arising from strong electromagnetic field coupling induced by adjacent Au NPs. The spot‐to‐spot SERS signals show that the relative standard deviation (RSD) in the intensity of the main Raman vibration modes (1310, 1361, 1509, 1650 cm^?1) of Rhodamine 6G at a concentration of 1 × 10^?10 M are consistently less than 20%, demonstrating good spatial uniformity and reproducibility. The SERS signals of sudan dye at a 1 × 10^?8 M concentration also shows high reproducibility with a low RSD of <20%. Further, the assembly substrate is stable, retaining excellent uniformity and sensitivity after storage for months. This assembly strategy integrating the advantages of low‐cost production, high sensitivity, and reproducibility would significantly facilitate practical SERS detection.     

Copper Nanoparticles Grafted on a Silicon Wafer and Their Excellent Surface‐Enhanced Raman Scattering

Copper nanoparticles grafted on a silicon wafer are fabricated by reducing copper ions with silicon–hydrogen bonds and assembling them in situ on the Si wafer. The nanoparticles, with an average size of 20 nm, grow uniformly and densely on the Si wafer, and they are used as substrates for surface‐enhanced Raman scattering. These substrates exhibit excellent enhancement in the low concentration detection (1 × 10^?9 M ) of rhodamine 6G with an enhancement factor (EF) of 2.29 × 10⁷ and a relative standard deviation (RSD) of <20%. They are also employed to detect sudan‐I dye with distinguished sensitivity and uniformity. The results are interesting and significant because Cu substrates are otherwise thought to be poor. These effects might provide new ways to think about surface‐enhanced Raman scattering based on Cu substrates.     

Arrays of Cone‐Shaped ZnO Nanorods Decorated with Ag Nanoparticles as 3D Surface‐Enhanced Raman Scattering Substrates for Rapid Detection of Trace Polychlorinated Biphenyls

A new, highly sensitive and uniform three‐dimensional (3D) hybrid surface‐enhanced Raman scattering (SERS) substrate has been achieved via simultaneously assembling small Ag nanoparticles (Ag‐NPs) and large Ag spheres onto the side surface and the top ends of large‐scale vertically aligned cone‐shaped ZnO nanorods (ZnO‐NRs), respectively. This 3D hybrid substrate manifests high SERS sensitivity to rhodamine and a detection limit as low as 10^?11 M to polychlorinated biphenyl (PCB) 77—a kind of persistent organic pollutants as global environmental hazard. Three kinds of inter‐Ag‐NP gaps in 3D geometry create a huge number of SERS “hot spots” that mainly contribute to the high SERS sensitivity. Moreover, the supporting chemical enhancement effect of ZnO‐NRs and the better enrichment effect ascribed to the large surface area of the substrate also help to achieve a lower detection limit. The arrays of cone‐shaped ZnO‐NRs decorated with Ag‐NPs on their side surface and large Ag spheres on the top ends have potentials in SERS‐based rapid detection of trace PCBs.     

High‐Density Hotspots Engineered by Naturally Piled‐Up Subwavelength Structures in Three‐Dimensional Copper Butterfly Wing Scales for Surface‐Enhanced Raman Scattering Detection

Very recently, wing scales of natural Lepidopterans (butterflies and moths) manifested themselves in providing excellent three dimensional (3D) hierarchical structures for surface‐enhanced Raman scattering (SERS) detection. But the origin of the observed enormous Raman enhancement of the analytes on 3D metallic replicas of butterfly wing scales has not been clarified yet, hindering a full utilization of this huge natural wealth with more than 175 000 3D morphologies. Herein, the 3D sub‐micrometer Cu structures replicated from butterfly wing scales are successfully tuned by modifying the Cu deposition time. An optimized Cu plating process (10 min in Cu deposition) yields replicas with the best conformal morphologies of original wing scales and in turn the best SERS performance. Simulation results show that the so‐called “rib‐structures” in Cu butterfly wing scales present naturally piled‐up hotspots where electromagnetic fields are substantially amplified, giving rise to a much higher hotspot density than in plain 2D Cu structures. Such a mechanism is further verified in several Cu replicas of scales from various butterfly species. This finding paves the way to the optimal scale candidates out of ca. 175 000 Lepidopteran species as bio‐templates to replicate for SERS applications, and thus helps bring affordable SERS substrates as consumables with high sensitivity, high reproducibility, and low cost to ordinary laboratories across the world.     

Tunable Enhancement of Raman Scattering in Graphene‐Nanoparticle Hybrids

The realization of graphene‐gold‐nanoparticle (G‐AuNP) hybrids is presented here through a versatile electrochemical approach, which allows the continuous tuning of the size and density of the particles obtainable on the graphene surface. Raman scattering from graphene, which is significantly enhanced in such hybrids, is systematically investigated as a function of the size and density of particles at the same location. In agreement with theory, it is shown that the Raman enhancement is tunable by varying predominantly the density of the nanoparticles. Furthermore, it is observed that the increase in Raman cross‐section and the strength of Raman enhancement varies as a function of the frequency of the vibrational mode, which may be correlated with the plasmonic fingerprint of the deposited AuNPs. In addition to this electromagnetic enhancement, support is found for a chemical contribution through the occurrence of charge transfer from the AuNPs onto graphene. Finally, G‐AuNP hybrids can be efficiently utilized as SERS substrates for the detection of specifically bound non‐resonant molecules, whose vibrational modes can be unambiguously identified. With the possibility to tune the degree of Raman enhancement, this is a platform to design and engineer SERS substrates to optimize the detection of trace levels of analyte molecules.     

Exploring How to Increase the Brightness of Surface‐Enhanced Raman Spectroscopy Nanolabels: The Effect of the Raman‐Active Molecules and of the Label Size

Due to the surface‐enhanced Raman scattering (SERS) effect, SERS labels based on noble‐metal nanoparticles loaded with Raman‐active molecules are good candidates for ultrasensitive multiplexed assays and in vitro/in vivo imaging. However, understanding how to maximize the brightness of such labels is of paramount importance for their widespread application. The effective differential Raman scattering cross‐section (dσ_R/dΩ) of SERS labels made of pegylated gold nanoparticles loaded with various Raman active molecules (Raman reporters) is studied. It is found that proper choice of the Raman reporter and of nanoparticle size can enhance the dσ_R/dΩ by several orders of magnitude. The experimental results are understood by considering the molecular cross‐section for resonant Raman scattering and the local electromagnetic enhancement factor (G_SERS) in the nearby of gold nanoparticles. These results are useful to guide the design of SERS labels with improved performances and to provide a reference for the comparison of the absolute value of the dσ_R/dΩ of SERS labels based on metal nanoparticles.     

Gold Nanoparticles Sliding on Recyclable Nanohoodoos—Engineered for Surface‐Enhanced Raman Spectroscopy

Robust, macroscopically uniform, and highly sensitive substrates for surface‐enhanced Raman spectroscopy (SERS) are fabricated using wafer‐scale block copolymer lithography. The substrate consists of gold nanoparticles that can slide and aggregate on dense and recyclable alumina/silicon nanohoodoos. Hot‐spot engineering is conducted to maximize the SERS performance of the substrate. The substrate demonstrates remarkably large surface‐averaged SERS enhancements, greater than 10⁷ (>10⁸ in hot spots), with unrivalled macroscopic signal uniformity as characterized by a coefficient of variation of only 6% across 4 cm. After SERS analyses, the nanohoodoos can be recycled by complete removal of gold via a one‐step, simple, and robust wet etching process without compromising performance. After eight times of recycling, the substrate still exhibits identical SERS performance in comparison to a new substrate. The macroscopic uniformity combined with recyclability at conserved high performance is expected to contribute significantly on the overall competitivity of the substrates. These findings show that the gold nanoparticles sliding on recyclable nanohoodoo substrate is a very strong candidate for obtaining cost‐effective, high‐quality, and reliable SERS spectra, facilitating a wide and simple use of SERS for both laboratorial and commercial applications.     

Plasmonic Self‐Propelled Nanomotors for Explosives Detection via Solution‐Based Surface Enhanced Raman Scattering

Nanomotors represent a class of artificial machines that span the chasm between molecular motors and bigger micromotors. Their importance lies in the fact that to effectively navigate and perform tasks in a biological environment without alerting the action of the immune system, the maximal size of the object has to be well below 200 nm. Fully nanosized gold/silver core/shell plasmonic nanomotors using the seeded growth wet chemical approach, which allows high scalability of synthesis of the nanomotors compared to planar substrate‐based methods, is presented. Using the nanoparticle tracking analysis, the catalysis driven enhanced diffusion of the plasmonic nanomotors in the presence of low concentrations of fuel is presented and shown that the prepared nanomotors are good candidates for a solution‐based surface‐enhanced Raman spectroscopy detection of picric acid, a typical explosive. In addition to the mentioned effects, ligand‐exchange is performed on the nanomotors to replace the surfactant with its thiolated analog, a combination which is already proven in literature to be stealthy to the immune response of the living organism.     

2D MXenes as a Promising Candidate for Surface Enhanced Raman Spectroscopy: State of the Art,Recent Trends,and Future Prospects

Surface-enhanced enhanced Raman spectroscopy (SERS) has emerged as a powerful analytical technique for ultrasensitive and label-free detection of chemical species, with numerous applications in various fields. Recently, 2D MXenes, have evoked substantial intrigue as promising substrates for SERS. Hence, a comprehensive understanding of the developments in the Raman effect and the mechanisms involved in SERS is highly crucial. The review reflects the advances, working principle, and dual mechanisms, including SERS's electromagnetic and chemical mechanisms. Noble metal nanostructures are highly prioritized as SERS substrates owing to their excellent sensitivity. However, due to certain disadvantages that they pose, metal-free SERS substrates with exceptional tunable properties are extensively researched in the current days. The combination of 2D MXenes and nanostructures can be effective in producing enhanced SERS signals. SERS performance of different MXene-based materials is emphasized. The performance of this combination is credited to their large surface-to-volume ratio, good electrical conductivity, and surface-terminated functionalities. The recent advancements in MXenes and MXenes-based heterostructures driven SERS sensing concerning the structural design of the material, its performance, and the mechanisms are studied. Finally, a detailed conclusion is provided with the challenges and future perspectives for designing 2D materials for efficient SERS sensors.     

Temperature‐Induced Stacking to Create Cu2O Concave Sphere for Light Trapping Capable of Ultrasensitive Single‐Particle Surface‐Enhanced Raman Scattering

The fabrication of bowl or concave particles with “asymmetric centers” has drawn considerable attentions, in which multiple scattering occurs inside the particles and the ability of light scattering is distinctly enhanced. However, the limited variety of templates, the uncontrollable dimensions such as the size of concavity and the complex growth process have posed serious limitations to the reproducible construction of concave particles with desired geometries and their light‐trapping properties. Herein, a “temperature‐induced stacking” strategy is proposed to create controllable concavity Cu₂O spheres for the first time. Different sizes of F68 micelles can be formed through aggregation under different reaction temperatures, which can serve as soft template to tailor concave geometries of Cu₂O spheres. The as‐prepared Cu₂O concave sphere (CS) can serve as single‐particle (SP) surface‐enhanced Raman scattering (SERS) substrate for highly repeatable and consistent Raman spectra. The unique cavity of Cu₂O CS entraps light effectively, which also enhances the scattering length owing to multiple light scattering. Combined with slightly increased surface area and charge‐transfer process, Cu₂O CS exhibits remarkable single‐particle SERS performance, with an ultralow low detection limit (2 × 10^?8 mol L^?1) and metal comparable enhancement factor (2.8 × 10⁵).     

Large‐Area Silver‐Coated Silicon Nanowire Arrays for Molecular Sensing Using Surface‐Enhanced Raman Spectroscopy

A new and facile method to prepare large‐area silver‐coated silicon nanowire arrays for surface‐enhanced Raman spectroscopy (SERS)‐based sensing is introduced. High‐quality silicon nanowire arrays are prepared by a chemical etching method and used as a template for the generation of SERS‐active silver‐coated silicon nanowire arrays. The morphologies of the silicon nanowire arrays and the type of silver‐plating solution are two key factors determining the magnitude of SERS signal enhancement and the sensitivity of detection; they are investigated in detail for the purpose of optimization. The optimized silver‐coated silicon nanowire arrays exhibit great potential for ultrasensitive molecular sensing in terms of high SERS signal enhancement ability, good stability, and reproducibility. Their further applications in rapidly detecting molecules relating to human health and safety are discussed. A 10 s data acquisition time is capable of achieving a limit of detection of approximately 4 × 10^?6 M calcium dipicolinate (CaDPA), a biomarker for anthrax. This value is 1/15 the infectious dose of spores (6 × 10^?5 M required), revealing that the optimized silver‐coated silicon nanowire arrays as SERS‐based ultrasensitive sensors are extremely suitable for detecting Bacillus anthracis spores.     

Micro‐/Nanostructured Highly Crystalline Organic Semiconductor Films for Surface‐Enhanced Raman Spectroscopy Applications

The utilization of inorganic semiconductors for surface‐enhanced Raman spectroscopy (SERS) has attracted enormous interest. However, despite the technological relevance of organic semiconductors for enabling inexpensive, large‐area, and flexible devices via solution processing techniques, these π‐conjugated systems have never been investigated for SERS applications. Here for the first time, a simple and versatile approach is demonstrated for the fabrication of novel SERS platforms based on micro‐/nanostructured 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) thin films via an oblique‐angle vapor deposition. The morphology of C8‐BTBT thin films is manipulated by varying the deposition angle, thus achieving highly favorable 3D vertically aligned ribbon‐like micro‐/nanostructures for a 90° deposition angle. By combining C8‐BTBT semiconductor films with a nanoscopic thin Au layer, remarkable SERS responses are achieved in terms of enhancement (≈10⁸), stability (>90 d), and reproducibility (RSD < 0.14), indicating the great promise of Au/C8‐BTBT films as SERS platforms. Our results demonstrate the first example of an organic semiconductor‐based SERS platform with excellent detection characteristics, indicating that π‐conjugated organic semiconductors have a great potential for SERS applications.     

Efficiency Enhancement of Single‐Walled Carbon Nanotube‐Silicon Heterojunction Solar Cells Using Microwave‐Exfoliated Few‐Layer Black Phosphorus

Carbon nanotube‐silicon (CNT‐Si)‐based heterojunction solar cells (HJSCs) are a promising photovoltaic (PV) system. Herein, few‐layer black phosphorus (FL‐BP) sheets are produced in N‐methyl‐2‐pyrrolidone (NMP) using microwave‐assisted liquid‐phase exfoliation and introduced into the CNTs‐Si‐based HJSCs for the first time. The NMP‐based FL‐BP sheets remain stable after mixing with aqueous CNT dispersion for device fabrication. Due to their unique 2D structure and p‐type dominated conduction, the FL‐BP/NMP incorporated CNT‐Si devices show an impressive improvement in the power conversion efficiency from 7.52% (control CNT‐Si cell) to 9.37%. Our density‐functional theory calculation reveals that lowest unoccupied molecular orbital (LUMO) of FL‐BP is higher in energy than that of single‐walled CNT. Therefore, we observed a reduction in the orbitals localized on FL‐BP upon highest occupied molecular orbital to LUMO transition, which corresponds to an improved charge transport. This study opens a new avenue in utilizing 2D phosphorene nanosheets for next‐generation PVs.     

Selective,Quantitative, and Multiplexed Surface‐Enhanced Raman Spectroscopy Using Aptamer‐Functionalized Monolithic Plasmonic Nanogrids Derived from Cross‐Point Nano‐Welding

Recent advances in surface‐enhanced Raman spectroscopy (SERS) have resulted in multiplexing with unprecedented levels of sensitivity and selectivity in trace‐amount detection. However, quantification of multiple trace‐amount molecules with ng‐level accuracy has yet to be demonstrated due to nonuniform distribution of SERS enhancement and random adsorption of molecules at low concentrations. While Raman reporter‐free SERS is favorable for quantification in that the unique fingerprint spectra of molecules enable specific molecular identification, it has yet to be demonstrated due to poor reproducibility and insufficient SERS enhancement. Raman reporter‐free multiplex SERS with highly accurate quantification is successfully realized by versatile aptamer‐functionalized plasmonic Au nanogrids with uniform SERS enhancement. By cross‐point nano‐welding, monolithic Au nanogrids with excellent uniformity and high stability in aqueous media are produced. Raman reporter‐free multiplex detection and highly accurate quantification of concentration and composition is realized at picomolar levels. As a demonstration, Au nanogrids functionalized with bisphenol A‐specific aptamers successfully detect and quantify trace‐amounts of bisphenol A (8.49 ng) from thermal receipt paper. Moreover, principal component analysis is applied to multiplex SERS spectra to establish a ternary composition map, which can potentially serve as a practical reference for future Raman reporter‐free SERS.     

Near‐Field Enhanced Plasmonic‐Magnetic Bifunctional Nanotubes for Single Cell Bioanalysis

Near‐field enhanced bifunctional plasmonic‐magnetic (PM) nanostructures consisting of silica nanotubes with embedded solid nanomagnets and uniformly dual‐surface‐coated plasmonic Ag nanoparticles (NPs) are rationally synthesized. The solid embedded sections of nanotubes provide single‐molecule sensitivity with an enhancement factor up to 7.2 × 10⁹ for surface‐enhanced Raman scattering (SERS). More than 2× SERS enhancement is observed from the hollow section compared to the solid section of the same nanotube. The substantial SERS enhancement on the hollow section is attributed to the dual‐sided coating of Ag NPs as well as the near‐field optical coupling of Ag NPs across the nanotube walls. Experimentation and modeling are carried out to understand the dependence of SERS enhancement on the NP sizes, junctions, and the near field effects. By tuning the aspect ratio of the embedded nanomagnets, the magnetic anisotropy of nanotubes can be readily controlled to be parallel or vertical to the long directions for nano‐manipulation. Leveraging the bifunctionality, a nanotube is magnetically maneuvered to a single living mammalian cell amidst many and its membrane composition is analyzed via SERS spectroscopy.     

利用纳米门电极增强拉曼散射

为了更好地了解表面增强拉曼光谱(SERS)的机制,并进一步提高增强因子,研制了具有高稳定性的纳米劈裂装置及芯片。结合纳米劈裂技术及SERS技术,在拉曼光谱测量的同时能非常精确地操纵两纳米电极间的距离以观察相应拉曼光谱强度的变化。发现拉曼光谱强度依赖于纳米电极的间距以及激光的偏振化方向。在利用两纳米电极作为增强体的基础上引入了纳米门电极,并观察偏置电压下的门电极对拉曼光谱信号的影响。实验结果表明,拉曼光谱信号的强度强烈地依赖于纳米门电极上所施加的偏置电压。实验为增强拉曼信号提供了新的方法,同时为拉曼光谱增强机制的理论研究提供了参考数据。     

Using SERS Tags to Image the Three‐Dimensional Structure of Complex Cell Models

Methods to image complex 3D cell cultures are limited by issues such as fluorophore photobleaching and decomposition, poor excitation light penetration, and lack of complementary techniques to verify the 3D structure. Although it remains insufficiently demonstrated, surface‐enhanced Raman scattering (SERS) imaging is a promising tool for the characterization of biological complex systems. To this aim, a controllable 3D cell culture model which spans nearly 1 cm² in surface footprint is designed. This structure is composed of fibroblasts containing SERS‐encoded nanoparticles (i.e., SERS tags), arranged in an alternating layered structure. This “sandwich” type structure allows monitoring of the SERS signals in the z‐axis and with mm dimensions in the xy‐axis. Taking advantage of correlative microscopy techniques such as electron microscopy, it is possible to corroborate nanoparticle positioning and distances in z‐depths of up to 150 µm. This study reveals a proof‐of‐concept method for detailed 3D SERS imaging of a complex, dense 3D cell culture model.