Fabrication and evolution of multilayer silver nanofilms for surface-enhanced Raman scattering sensing of arsenate

Surface-enhanced Raman scattering (SERS) has recently been investigated extensively for chemical and biomolecular sensing. Multilayer silver (Ag) nanofilms deposited on glass slides by a simple electroless deposition process have been fabricated as active substrates (Ag/GL substrates) for arsenate SERS sensing. The nanostructures and layer characteristics of the multilayer Ag films could be tuned by varying the concentrations of reactants (AgNO₃/BuNH₂) and reaction time. A Ag nanoparticles (AgNPs) double-layer was formed by directly reducing Ag⁺ ions on the glass surfaces, while a top layer (3rd-layer) of Ag dendrites was deposited on the double-layer by self-assembling AgNPs or AgNPs aggregates which had already formed in the suspension. The SERS spectra of arsenate showed that characteristic SERS bands of arsenate appear at approximately 780 and 420 cm^-1, and the former possesses higher SERS intensity. By comparing the peak heights of the approximately 780 cm^-1 band of the SERS spectra, the optimal Ag/GL substrate has been obtained for the most sensitive SERS sensing of arsenate. Using this optimal substrate, the limit of detection (LOD) of arsenate was determined to be approximately 5 μg·l^-1.     

Plasmonic Core–Shell–Satellites with Abundant Electromagnetic Hotspots for Highly Sensitive and Reproducible SERS Detection

In this work, we develop a Ag@Al₂O₃@Ag plasmonic core–shell–satellite (PCSS) to achieve highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) detection of probe molecules. To fabricate PCSS nanostructures, we employ a simple hierarchical dewetting process of Ag films coupled with an atomic layer deposition (ALD) method for the Al₂O₃ shell. Compared to bare Ag nanoparticles, several advantages of fabricating PCSS nanostructures are discovered, including high surface roughness, high density of nanogaps between Ag core and Ag satellites, and nanogaps between adjacent Ag satellites. Finite-difference time-domain (FDTD) simulations of the PCSS nanostructure confirm an enhancement in the electromagnetic field intensity (hotspots) in the nanogap between the Ag core and the satellite generated by the Al₂O₃ shell, due to the strong core–satellite plasmonic coupling. The as-prepared PCSS-based SERS substrate demonstrates an enhancement factor (EF) of 1.7 × 10⁷ and relative standard deviation (RSD) of ~7%, endowing our SERS platform with highly sensitive and reproducible detection of R6G molecules. We think that this method provides a simple approach for the fabrication of PCSS by a solid-state technique and a basis for developing a highly SERS-active substrate for practical applications.     

Enhanced sensitivity of a direct SERS technique for Hg(2+) detection based on the investigation of the interaction between silver nanoparticles and mercury ions

Mercury which is a very important pollutant has drawn significant attention in recent research. So far, among the various detection methods, the strategies based on surface-enhanced Raman scattering (SERS) are quite attractive because of the high sensitivity, and especially as it is reported that Hg(2+) can be directly detected by SERS without tagging. However, the procedure for the direct SERS detection of mercury is still unclear with little experimental evidence, limiting further development of Hg(2+) detection by SERS. Herein, we performed a simple method based on SERS for the detection of mercury ions in water without tagging. It is established that in only 2 min, low concentration of Hg(2+) can be recognized based on the decrease of SERS intensity. The detection procedure is investigated by multiple characterizations and the mechanism proven by the obtained data provides a practical way to further improve the sensitivity of the SERS detection. It is demonstrated that the interaction between Hg(2+) and Ag nanoparticles (Ag NPs) could occur in a short time, which includes the complexation of Hg(2+) with citrate and the formation of amalgam due to the reduction of Hg(2+). This interaction influences the surface plasmon resonance (SPR) property of Ag NPs and thereby decays the electromagnetic enhancement of Ag NPs; meanwhile the interaction also causes the zeta potential decrease of Ag NPs and accordingly affects the adsorption of Raman reporter molecules on the surface of Ag NPs. Therefore, the weakness of SERS intensity in the presence of Hg(2+) should be mainly attributed to the interaction between Hg(2+) and Ag NPs. From the mechanism demonstrated, it can be speculated that using fewer Ag NPs in the detection could improve the sensitivity, because at low Hg(2+) concentration the interaction becomes stronger since every Ag nanoparticle acts with more Hg(2+) ions. Accordingly, we establish that 90.9 pM (18.2 ppt) Hg(2+) is detected in 18 μM Ag NPs, which is much lower than that in reported papers.     

High-density metallic nanogaps fabricated on solid substrates used for surface enhanced Raman scattering

The Raman signal of adsorbed molecules can be significantly enhanced by utilizing metallic structures with high-density Raman hot spots used as surface enhanced Raman scattering (SERS) substrates. In this work, we develop a simple, convenient and tunable method to fabricate high-density Ag or Au nanogaps on Si wafers. These nanogaps can serve as Raman hot spots, leading to dramatic enhancement of the Raman signal. The high-density nanogaps can be formed by repeating the electroless deposition of Ag NPs (or Au NPs) and coating of p-aminothiophenol (PATP, a Raman probe) on the deposited Ag NPs (or Au NPs) through the self-assembly process. After removal of PATP by O(2) plasma, the as-fabricated SERS substrate can be reused for the detection of other molecules.     

Improved surface-enhanced Raman scattering based on Ag-Au bimetals prepared by galvanic replacement reactions

In this work, the improved surface-enhanced Raman scattering (SERS) of Rhodamine 6G (R6G) adsorbed on Ag-Au bimetals synthesized via galvanic replacement of Ag with Au was first investigated. First, silver substrates were roughened by triangular-wave oxidation-reduction cycles (ORC) in aqueous solutions containing 0.1 M KCl. At the same time, Cl⁻ and Au-containing nanocomplexes in solutions were prepared by treating gold substrates with the similar electrochemically roughening procedures. Then the roughened Ag substrates were incubated in the Cl⁻ and Au-containing solutions for different couples of minutes to undergo the galvanic replacement reactions. Encouragingly, the SERS of R6G adsorbed on this roughened Ag substrate modified by the replacement of Ag with Au for 3 min exhibits a higher intensity by one order of magnitude and a better resolution, as compared with the SERS of R6G adsorbed on an unmodified roughened Ag substrate. The increased SERS effect can be ascribed to the compositions of complexes formed on the substrates. In this optimum condition, the atomic ratio of Ag to Au is ca. 6.6.     

负载有Ag纳米粒子的TiO2准一维复合材料制备及其SERS效应

采用紫外光还原法和种子法制得了不同含量Ag纳米粒子负载的锐钛矿型TiO2纳米带复合材料。用各种测试技术对产物的物相、形貌、Ag负载情况以及SERS性质进行了一系列表征。测试结果表明,以紫外光还原法获得的产物中Ag完全负载在TiO2纳米带表面,其粒径主要处在10～50 nm间,且Ag负载量随着还原次数增多而缓慢增加。在此基础上,以种子法制得的产物中Ag负载量则显著增大,覆盖率可达80 %以上。这种含Ag纳米复合材料具有检测吡啶分子的SERS活性,其Ag负载量越多,SERS效应越明显。     

Growth of silver nanowires on GaAs wafers

Silver (Ag) nanowires with chemically clean surfaces have been directly grown on semi-insulating gallium arsenide (GaAs) wafers through a simple solution/solid interfacial reaction (SSIR) between the GaAs wafers themselves and aqueous solutions of silver nitrate (AgNO(3)) at room temperature. The success in synthesis of Ag nanowires mainly benefits from the low concentration of surface electrons in the semi-insulating GaAs wafers that can lead to the formation of a low-density of nuclei that facilitate their anisotropic growth into nanowires. The resulting Ag nanowires exhibit rough surfaces and reasonably good electric conductivity. These characteristics are beneficial to sensing applications based on single-nanowire surface-enhanced Raman scattering (SERS) and possible surface-adsorption-induced conductivity variation.     

Improved surfaced-enhanced Raman scattering based on electrochemically roughened silver substrates modified through argon plasma treatment

A new surface-enhanced Raman scattering (SERS)-active silver substrate has been developed by using a combination of electrochemical triangular-wave oxidation/reduction cycles (ORCs) and argon plasma treatment to roughen the substrate, increasing its SERS effect. In the first step, a mechanically polished Ag substrate was roughened through triangular-wave ORCs in an aqueous solution containing 0.1 M KCl. Next, the electrochemically roughened Ag substrate was treated with radio frequency-excited Ar plasma. 2,2′-Bipyridine (Bipy) was used as a Raman probe to evaluate the SERS enhancement provided by the new Ag substrate. Encouragingly, we found that the SERS intensity of Bipy increased up to sevenfold, with the SERS spectrum of Bipy exhibiting better resolution, when using the fully treated Ag substrate, relative to the use of an electrochemically ORCs-treated Ag substrate that had not been subjected to plasma treatment. The improved SERS effects were related to the coalescence of grains and hills as well as to the formation of dells and pits during the electrochemical ORCs and Ar plasma roughening processes.     

Nanostructured Tin Oxide as a Surface‐Enhanced Raman Scattering Substrate for the Detection of Nitroaromatic Compounds

Sensing of low concentrations of two nitroaromatic compounds, 1,2‐dinitrotoluene and 2‐nitrophenol, is presented. The sensing mechanism is based on surface‐enhanced Raman scattering (SERS) using nanostructured tin oxide as the SERS‐active substrate. The SnO_x nanostructures are synthesized by a simple solgel method and doped with Ag and Au. The Raman signal of a low concentration of the analyte, otherwise extremely weak, becomes significant when the analytes are attached to these substrates. Doping of SnO_x nanopowders with Ag and Au leads to a further increase in the Raman intensities. This study demonstrates the scope of ceramic–metal nanocomposites as convenient solid‐state SERS sensors for low‐level detection.     

Thermal and mechanical properties of polyamide 12/graphene nanoplatelets nanocomposites and parts fabricated by fused deposition modeling

The printable polyamide 12 (PA12) nanocomposite filaments with 6 wt % graphene nanoplatelets (GNPs) for fused deposition modeling (FDM) were prepared by melting compounding and smoothly printed via a commercial FDM three‐dimensional (3D) printer. The thermal conductivity (λ) and elastic modulus (E) of 3D printed PA12/GNPs parts along to the printing direction had an increase by 51.4% and 7% than that of compression molded parts, which is due to the GNPs preferentially aligning along to the printing direction. Along with these improved properties, ultimate tensile strength of 3D printed PA12/GNPs parts was well maintained. These results indicate that FDM is a new way to achieve PA12/GNPs parts with enhanced λ over compression moulding, which could contribute to realize efficient and flexible heat management for a wide range of applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45332.     

Multiple depositions of Ag nanoparticles on chemically modified agarose films for surface-enhanced Raman spectroscopy

A facile and cost-effective approach for the preparation of a surface-enhanced Raman spectroscopy (SERS) substrate through constructing silver nanoparticle/3-aminopropyltriethoxysilane/agarose films (Ag NPs/APTES/Agar film) on various solid supports is described. The SERS performance of the substrate was systematically investigated, revealing a maximum SERS intensity with four layers of the Ag NP deposition. The enhancement factor of the developed substrate was calculated as 1.5 × 10(7) using rhodamine 6G (R6G) as the probe molecule, and the reproducibility of the SERS signals was established. A high throughput screening platform was designed, manufactured and implemented which utilised the ability to cast agarose to assemble arrays. Quantitative analysis of 4-aminobenzoic acid (4-ABA) and 4-aminothiophenol (4-ATP) was achieved over a ～0.5 nM-0.1 μM range.     

Synthesis and characterization of coaxial silver/silica/polypyrrole nanocables

Double‐shelled coaxial nanocables of silver nanocables with SiO₂ and polypyrrole (PPy; Ag/SiO₂/PPy) were synthesized by a simple method. The thickness of the outer PPy shell could be controlled by the amount of pyrrole monomer. The silver nanocables encapsulated in the interior of the hollow PPy nanotubes were obtained by the removal of the midlayer SiO₂. By the silver‐mirror reaction, flowerlike Ag nanostructures could be formed on the surface of the Ag/SiO₂/PPy multilayer nanocable. The application of the as‐prepared Ag/SiO₂/PPy–Ag composites in surface‐enhanced Raman scattering (SERS) was studied with Rhodamine B (Rh B) as a probe molecule. We found that the composites could be used as SERS substrates and that they exhibited excellent enhancement ability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Micro/nano-structured graphitic carbon nitride–Ag nanoparticle hybrids as surface-enhanced Raman scattering substrates with much improved long-term stability

Surface-enhanced Raman scattering (SERS) substrates with high SERS activity and stability are important for SERS sensors. A facile method was developed to fabricate efficient and stable SERS substrates by combining Ag nanoparticles (NPs) and micro-scale sheeted graphitic carbon nitride (g-C₃N₄). The g-C₃N₄/Ag NPs hybrid could provide a great number of hot spots and concentrated the analyte by the π–π stacking interaction between analyte molecules and g-C₃N₄, making a dramatic Raman enhancement. Moreover, the g-C₃N₄/Ag NPs hybrid uniformly immobilized Ag NPs on the surface and edges of g-C₃N₄ sheets by an interaction between Ag NPs and g-C₃N₄, leading to much improved long-term stability. This could be explained in terms of the electron–donor effect of g-C₃N₄, which was further confirmed by density functional theory calculations. The inherent Raman enhancing effect of g-C₃N₄ itself also contributed to the total SERS responses. Due to multiple enhancement contributions, the g-C₃N₄/Ag NPs hybrid exhibited a strong Raman enhancement effect for with an enhancement factor of 4.6 × 10⁸ (evaluated by using crystal violet as a probe), and possessed wide adaptability from dyes, pesticides to bio-molecules.     

Functional hybrid nickel nanostructures as recyclable SERS substrates: detection of explosives and biowarfare agents

We present the synthesis of highly anisotropic nickel nanowires (NWs) and large area, free-standing carpets extending over cm(2) area by simple solution phase chemistry. The materials can be post-synthetically manipulated to produce hybrid tubes, wires, and carpets by galvanic exchange reactions with Au(3+), Ag(+), Pt(2+), and Pd(2+). All of these structures, especially the hybrid carpets and tubes, have been prepared in bulk and are surface enhanced Raman scattering (SERS) active substrates. Molecules of relevance such as dipicolinic acid (constituting 5-15% of the dry weight of bacterial spores of Bacillus anthracis), dinitrotoluene, hexahydro-1,3,5-triazine (RDX), and trinitrotoluene at nanomolar concentrations have been detected. An enhancement factor of ～10(10) was observed for the Ni-Au nanocarpet. The reusability of the Ni-Au nanocarpet for SERS applications was tested 5 times without affecting the sensitivity. The reusability and sensitivity over large area have been demonstrated by Raman microscopy. Our method provides an easy and cost effective way to produce recyclable, large area, SERS active substrates with high sensitivity and reproducibility which can overcome the limitation of one-time use of traditional SERS substrates.     

基于Ostwald ripening自组装工艺的银纳米颗粒活性衬底的高稳定性

利用Ostwald ripening自组装工艺对拉曼增强衬底进行处理,得到粒径和密度不同的银纳米颗粒拉曼增强衬底。用龙胆紫生物大分子作为探针,对其表面增强拉曼散射（SERS）和表面增强荧光（SEF）进行研究发现,拉曼和荧光光谱强度存在着相似的变化趋势,且随着自组装工艺时间的递增,强度的变化趋于稳定。研究结果表明：Ostwald ripening自组装工艺可以优化SERS和SEF增强效果及其稳定性,故其可为研制具有长期稳定性、低成本的基于SERS和SEF效应生物化学传感器件提供研究基础。     

Preparation of α-Fe2O3/Ag core/shell nanocomposites and SERS properties

用籽晶法,以甲醛为还原剂、3-氨丙基三乙氧基硅烷(APS)为改性剂,在Ag［(NH₃)₂］⁺溶液中制备α-Fe₂O₃/Ag核壳结构复合粉体。采用XRD、TEM和EDX对样品进行表征,系统研究了APS改性剂、醇水比等对复合纳米颗粒包覆效果及性能的影响;并用吡啶(Py)为探针,研究了α-Fe₂O₃/Ag核壳纳米颗粒作为拉曼衬底时的拉曼增强性能相似文献   

Preparation,friction, wear,and fracture of the Si3N4-Ag-GNPs composites prepared by SPS

Silver and graphene nanoplatelets (Ag-GNPs) have been employed as reinforcements to prepare the self-lubricating silicon nitride matrix composites via 3D ball milling (Turbula) and spark plasma sintering. The prepared composites were characterized by scanning electron microscope with energy dispersive spectroscopy, Vickers hardness tester and reciprocating ball tribometer. Fracture surface morphology of the sintered composites indicated the potential reinforcement by the ductile silver phase. The mechanical property testing revealed that Si₃N₄ composites with Ag and GNPs incorporation exhibited lower hardness and slightly lower toughness compared with Si₃N₄ monolithic material. However, the coefficient of friction and wear in composites exhibited the lower values in 1 N friction force testing range.     

Hydrogel-Assisted 3D Volumetric Hotspot for Sensitive Detection by Surface-Enhanced Raman Spectroscopy

Effective hotspot engineering with facile and cost-effective fabrication procedures is critical for the practical application of surface-enhanced Raman spectroscopy (SERS). We propose a SERS substrate composed of a metal film over polyimide nanopillars (MFPNs) with three-dimensional (3D) volumetric hotspots for this purpose. The 3D MFPNs were fabricated through a two-step process of maskless plasma etching and hydrogel encapsulation. The probe molecules dispersed in solution were highly concentrated in the 3D hydrogel networks, which provided a further enhancement of the SERS signals. SERS performance parameters such as the SERS enhancement factor, limit-of-detection, and signal reproducibility were investigated with Cyanine5 (Cy5) acid Raman dye solutions and were compared with those of hydrogel-free MFPNs with two-dimensional hotspots. The hydrogel-coated MFPNs enabled the reliable detection of Cy5 acid, even when the Cy5 concentration was as low as 100 pM. We believe that the 3D volumetric hotspots created by introducing a hydrogel layer onto plasmonic nanostructures demonstrate excellent potential for the sensitive and reproducible detection of toxic and hazardous molecules.     

Application of In Situ Surface-Enhanced Raman Spectroscopy (SERS) to the Study of Citrate Oxidation on Silica-Supported Silver Nanoparticles

Surface-enhanced Raman spectroscopy (SERS) was used to characterize citrate anions adsorbed on nanometer-sized particles of Ag supported on SiO₂. The magnitude of the surface-enhancement effect was determined to be ～3 × 10² on the as-prepared samples of Ag/SiO₂. Upon heating in air above 373 K, the citrate anions undergo oxidation to uni- and bidentate carbonate species and then decomposition to CO₂ and adsorbed O atoms. In the SERS of Ag/SiO₂, a very strong enhancement of the ν(C=O) signal for the bidentate CO₃ species was observed for temperatures between 398 and 448 K, which is accompanied by an increase in the UV–vis absorbance of the sample at the frequency of the laser line used for Raman spectroscopy. This phenomenon is attributed to an increase in the surface-enhancement effect caused by clustering of the Ag nanoparticles as they sinter at elevated temperatures. The present investigation shows that the proper interpretation of in situ SERS spectra requires an understanding of the changes occurring in the UV–vis spectrum of the sample.     

Additive Manufacturing-Enabled Architected Nanocomposite Lattices Coated with Plasmonic Nanoparticles for Water Pollutants Detection

Novel low-cost materials to uptake and detect vestigial amounts of pesticides are highly desirable for water quality monitoring. Herein, are demonstrated, for the first time, surface-enhanced Raman scattering (SERS) sensors enabled via additively manufactured lattices coated with plasmonic nanoparticles (NPs) for detecting pesticides in real water samples. The architected lattices comprising polypropylene (PP) and multiwall carbon nanotubes (MWCNTs) are realized via fused filament fabrication (FFF). In the first stage, the SERS performance of the PP/MWCNT filaments coated with distinct metallic NPs (Ag NPs and Au NPs) is evaluated using methylene blue (MB) as molecular probe. Thereafter, distinctly architected hybrid SERS sensors with periodic porous and fully dense geometries are investigated as adsorbents to uptake MB from aqueous solutions and subsequent detection using SERS. The spatial distribution of MB and Ag NPs on the FFF-printed lattices is accomplished by SERS imaging. The best hybrid composite is used as SERS probing system to detect low amounts of pesticides (thiram and paraquat) and offers a detection limit of 100 nm for both pesticides. As a proof-of-concept, FFF-enabled test strips are used to detect in loco paraquat molecules spiked on real water samples (Estuary Aveiro water and tap water) using a portable Raman spectrometer.