Multifunctional Au‐Coated TiO2 Nanotube Arrays as Recyclable SERS Substrates for Multifold Organic Pollutants Detection

A multifunctional Au‐coated TiO₂ nanotube array is made via synthesis of a TiO₂ nanotube array through a ZnO template, followed by deposition of Au particles onto the TiO₂ surface using photocatalytic deposition and a hydrothermal method, respectively. Such arrays exhibit superior detection sensitivity with high reproducibility and stability. In addition, due to possessing stable catalytic properties, the arrays can clean themselves by photocatalytic degradation of target molecules adsorbed to the substrate under irradiation with UV light into inorganic small molecules using surface‐enhanced Raman spectroscopy (SERS) detection, so that recycling can be achieved. Finally, by detection of Rhodamine 6G (R6G) dye, herbicide 4‐chlorophenol (4‐CP), persistent organic pollutant (POP) dichlorophenoxyacetic acid (2,4‐D), and organophosphate pesticide methyl‐parathion (MP), the unique recyclable properties indicate a new route in eliminating the single‐use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants.     

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.     

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.     

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.     

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.     

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.     

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.     

Gold Nanoparticles and g‐C3N4‐Intercalated Graphene Oxide Membrane for Recyclable Surface Enhanced Raman Scattering

Toxic organic pollutants in the aquatic environment cause severe threats to both humans and the global environment. Thus, the development of robust strategies for detection and removal of these organic pollutants is essential. For this purpose, a multifunctional and recyclable membrane by intercalating gold nanoparticles and graphitic carbon nitride into graphene oxide (GNPs/g‐C₃N₄/GO) is fabricated. The membranes exhibit not only superior surface enhanced Raman scattering (SERS) activity attributed to high preconcentration ability to analytes through π–π and electrostatic interactions, but also excellent catalytic activity due to the enhanced electron–hole separation efficiency. These outstanding properties allow the membrane to be used for highly sensitive detection of rhodamine 6G with a limit of detection of 5.0 × 10^?14m and self‐cleaning by photocatalytic degradation of the adsorbed analytes into inorganic small molecules, thus achieving recyclable SERS application. Furthermore, the excellent SERS activity of the membrane is demonstrated by detection of 4‐chlorophenol at less than nanomolar level and no significant SERS or catalytic activity loss was observed when reusability is tested. These results suggest that the GNPs/g‐C₃N₄/GO membrane provides a new strategy for eliminating traditional, single‐use SERS substrates, and expands practical SERS application to simultaneous detection and removal of environmental pollutants.     

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.     

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.     

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.     

Alloy Engineering in Few‐Layer Manganese Phosphorus Trichalcogenides for Surface‐Enhanced Raman Scattering

Manganese phosphorus trichalcogenides are widely used in the field of photocatalysis and magnetic studies due to their broadband gaps. Herein, an alloy engineering method for the few‐layer manganese phosphorus trichalcogenides (MnPS_3–xSe_x, 0 ≤ x ≤ 3) in surface‐enhanced Raman scattering (SERS) is reported. A new strategy, with the coupling of exciton resonance (µ_ex) and photoinduced charge transfer (PICT), is applied to screen out materials for SERS enhancement. According to the calculation of density functional theory, the bandgap of manganese phosphorus trichalcogenides (MnPS₃) can be adjusted to match the band energy of Rhodamine 6G molecules by alloy engineering. Furthermore, a series of few‐layer MnPS_3–xSe_x (0 ≤ x ≤ 3) are fabricated to study the PICT‐induced SERS behavior under resonance excitation. The good performance with a detection limit down to 10^?9 m indicates that the synergistic resonances between µ_ex and PICT are crucial to the enhancement.     

Supported Faceted Gold Nanoparticles with Tunable Surface Plasmon Resonance for NIR‐SERS

A novel dry plasma methodology for fabricating directly stabilized substrate‐supported gold nanoparticle (NP) ensembles for near infrared surface enhanced Raman scattering (NIR SERS) is presented. This maskless stepwise growth exploits Au‐sulfide seeds by plasma sulfidization of gold nuclei to produce highly faceted Au NPs with a multiple plasmon resonance that can be tuned from the visible to the near infrared, down to 1400 nm. The role of Au sulfidization in modifying the dynamics of Au NPs and of the corresponding plasmon resonance is discussed. The tunability of the plasmon resonance in a broad range is shown and the effectiveness as substrates for NIR SERS is demonstrated. The SERS response is investigated by using different laser sources operating both in the visible and in the NIR. SERS mapping of the SERS enhancement factor is carried out in order to evaluate their effectiveness, stability, and reproducibility as NIR SERS substrates, also in comparison with gold NPs fabricated by conventional sputtering and with the state‐of‐the‐art in the current literature.     

基于表面增强拉曼光谱的甲萘威水溶液检测分析

以表面增强试剂OTR202和OTR103作为表面增强拉曼光谱(SERS)的活性基底,探索建立甲萘威水溶液的SERS检测方法。首先对比分析了甲萘威水溶液的普通拉曼光谱与SERS。然后分析了表面增强试剂与待测样本的加入量对甲萘威水溶液的SERS的影响。最后分析了质量浓度在0.1~15.0 mg/L范围内的甲萘威水溶液的SERS,并以1374 cm-1处的特征峰强度与甲萘威水溶液浓度进行线性回归,得到线性方程为y=414.5x+481.59,决定系数R2=0.9864。试验结果表明该研究方法对甲萘威水溶液的检测限可达到0.1 mg/L,说明以表面增强试剂OTR202和OTR103为SERS活性基底的SERS检测方法可用于水中甲萘威残留检测。     

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.     

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).     

Facile Fabrication of High‐Density Sub‐1‐nm Gaps from Au Nanoparticle Monolayers as Reproducible SERS Substrates

The fabrication of ultrasmall nanogaps (sub‐1 nm) with high density is of significant interest and importance in physics, chemistry, life science, materials science, surface science, nanotechnology, and environmental engineering. However, it remains a challenge to generate uncovered and clean sub‐1‐nm gaps with high density and uniform reproducibility. Here, a facile and low‐cost approach is demonstrated for the fabrication of high‐density sub‐1‐nm gaps from Au nanoparticle monolayers as reproducible surface‐enhanced Raman scattering (SERS) substrates. Au nanoparticles with larger diameters possess lower surface charge, thus the obtained large‐area nanoparticle monolayer generates a high‐density of sub‐1‐nm gaps. In addition, a remarkable SERS performance with a 10¹¹ magnitude for the Raman enhancement is achieved for 120 nm Au nanoparticle monolayers due to the dramatic increase in the electromagnetic field enhancement when the obtained gap is smaller than 0.5 nm. The Au nanoparticle monolayer is also transferred onto a stretchable PDMS substrate and the structural stability and reproducibility of the high‐density sub‐1‐nm gaps in Au monolayer films are illustrated. The resultant Au nanoparticle monolayer substrates with an increasing particle diameter exhibit tunable plasmonic properties, which control the plasmon‐enhanced photocatalytic efficiency for the dimerization of p‐aminothiophenol. The findings reported here offer a new opportunity for expanding the SERS application.     

Surface‐Activated Nanoparticles for Controlled Light‐Responsiveness

Most of the optical properties of nanoparticles (NPs) depend on a nonadditive effect, where there is a maximum (or optimum) value at a specific distance from the NP surface (proximity length). However, knowledge on the relation between the specific surface layer and light responsiveness of NPs is limited. In this study, surface properties of NPs are modulated by electron beam (e‐beam) treatment together with ionic control of the NP surface and dispersing media. The surface modification in terms of the proximity length is found to be critical to the selective enhancement of light absorbance in the ultraviolet‐visible (UV‐vis) and terahertz (THz) regions. In particular, the non‐temporarily electron‐activated NPs absorb short wavelength UV‐vis light, rendering them particulary advantageous for solar energy use. The control over the physical properties of general light‐responsive NPs is a new approach to designing solar‐energy‐based technologies.     

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。