SERS and FDTD simulation of gold nanoparticles grafted on germanium wafer via galvanic displacement

Uniform and dense Au nanoparticles grown on Ge (Au/Ge) were fabricated by a facile galvanic displacement method and employed as surface‐enhanced Raman scattering (SERS) substrates. The substrates exhibited excellent reproducibility in the detection of rhodamine 6G aqueous solution with a relative standard deviation of <20%. The substrate showed a high Raman enhancement factor of 3.44 × 10⁶. This superior SERS sensitivity was numerical confirmed by the three‐dimensional finite‐difference time‐domain method, which demonstrated a stronger electric field intensity (|E/E₀|²) distribution around the Au nanoparticles grown on Ge. This facile and low‐cost prepared Au/Ge substrate with high SERS sensitivity and reproducibility might have potential applications in monitoring in situ reaction in aqueous solution. Copyright © 2014 John Wiley & Sons, Ltd.     

Au Nanowire–Au Nanoparticles Conjugated System which Provides Micrometer Size Molecular Sensors

We report a new type of molecular sensor using a Au nanowire (NW)–Au nanoparticles (NPs) conjugated system. The Au NW–NPs structure is fabricated by the self‐assembly of biotinylated Au NPs on a biotinylated Au NW through avidin; this creates hot spots between NW and NPs that strongly enhance the Raman signal. The number of the Au NPs attached to the NW is reproducibly proportional to the concentration of the avidin, and is also proportional to the measured surface‐enhanced Raman scattering (SERS) signals. Since this well‐defined NW–NPs conjugated sensor is only a few micrometer long, we expect that development of multiplex nanobiosensor of a few tens micrometer size would become feasible by combining individually modified multiple Au NWs together on one substrate.     

银/金纳米线阵列表面增强拉曼基底的制备及对孔雀石绿的高灵敏度检测

利用种子介导的软模板生长方法制备了金纳米线(Au NWs)阵列, 通过调节生长温度控制Au NWs阵列的形貌, 最后在经硼氢化钠(NaBH₄)清洗过的Au NWs阵列上化学沉积银纳米颗粒(Ag NPs), 制得银/金纳米线(Ag/Au NWs)阵列作为表面增强拉曼散射(SERS)基底. 选用罗丹明6G(R6G)作为拉曼探针分子测定了Ag/Au NWs阵列的SERS性能. 结果表明, Ag/Au NWs阵列作为SERS基底具有高灵敏度、 优异的信号均匀性和良好的稳定性. 使用Ag/Au NWs阵列对孔雀石绿(MG)检测的检出限可低至1×10^-8 mol/L, 线性范围为 1×10^-8~1×10^-4 mol/L. NaBH₄可以在不影响SERS性能的情况下去除Ag/Au NWs阵列上吸附的分子, 使得 SERS基底可以重复使用. 使用Ag/Au NWs阵列对湖水中的MG进行检测, 得到了可靠的回收率, 证明Ag/Au NWs 阵列在检测环境水体中的孔雀石绿上具有应用潜力.     

Self‐Assembled Au Nanoparticles as Substrates for Surface‐Enhanced Vibrational Spectroscopy: Optimization and Electrochemical Stability

Three‐dimensional nanostructured metallic substrates for enhanced vibrational spectroscopy are fabricated by self‐assembly. Nanostructures consisting of one to 20 depositions of 13 nm‐diameter Au nanoparticles (NPs) on Au films are prepared and characterized by means of AFM and UV/Vis reflection–absorption spectroscopy. Surface‐enhanced polarization modulation infrared reflection–absorption spectroscopy (PM‐IRRAS) is observed from Au NPs modified by the probe molecule 4‐hydroxythiophenol. The limitation of this kind of substrate for surface‐enhanced PM‐IRRAS is discussed. The surface‐enhanced Raman scattering (SERS) from the same probe molecule is also observed and the effect of the number of Au‐NP depositions on the SERS efficiency is studied. The SERS signal from the probe molecule maximizes after 11 Au‐NP depositions, and the absolute SERS intensities from different batches are reproducible within 20 %. In situ electrochemical SERS measurements show that these substrates are stable within the potential window between ?800 and +200 mV (vs. Ag/AgCl/sat. Cl^?).     

Characteristics of Ga and Ag-doped ZnO-based nanowires for an ethanol gas sensor prepared by hot-walled pulsed laser deposition

Pure ZnO and Ga (3 % w/w) and Ag (3 % w/w)-doped ZnO nanowires (NWs) have been grown by use of the hot-walled pulse laser deposition technique. The doping characteristics of Ga and Ag in ZnO NWs were analyzed by use of photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS) and the results were compared with those for pure ZnO NWs. We also fabricated gas sensors by use of pure ZnO and Ga and Ag-doped ZnO NWs. Among the NW sensors, the Ag-doped NW sensor was most sensitive. We synthesized the NWs on sapphire substrates under different conditions, for example temperature, time, gas flow, and distance between target and substrate. The diameter and length of NWs were <100 nm and several microns, respectively. To analyze the effect of Ag doping on ZnO NWs, we investigated the near band edge emission by use of low-temperature PL and XPS. Significant changes in resistance and sensitivity were observed. When the sensors were used at 300 °C for detection of 1 ppm ethanol vapor, the sensitivity of the pure ZnO and the Ga and Ag-doped ZnO NW gas sensors was 97, 48, and 203 %, respectively.     

Preparation of Ag Nanowire @ Au Nanoparticle Hybrid Nanowires and their Influence on the Fluorescence Properties of P3HT

In this study, the galvanic displacement reaction between silver and AuCl₄⁻ was carried out to synthesize a series of silver nanowire (Ag NW) @ gold nanoparticle (Au NP) hybrid nanowires. The influence of Ag NW @ Au NP hybrid nanowires on the fluorescence properties of the poly (3‐hexylthiophene) (P3HT) was investigated. The particle sizes of Au NPs on the hybrid nanowires could be adjusted by varying the reaction time and the concentration of the HAuCl₄ solution. Furthermore, steady‐state fluorescence measurements showed that the fluorescence intensity of the P3HT films was higher on various Ag NW @ Au NP hybrid nanowires compared to that on a bare silicon substrate. This was due to the increase in the intensity of electromagnetic field by the localized surface plasmon resonances of Au NPs and surface plasmon polaritons of Ag NWs from the hybrid nanowires. The results were further confirmed by the Raman spectra of the P3HT films on different substrates.     

Stereoaligned Epitaxial Growth of Single‐Crystalline Platinum Nanowires by Chemical Vapor Transport

Epitaxial Pt nanowire (NW) arrays are synthesized for the first time by a chemical vapor transport method by using a metal halide as a precursor. Here we report that the epitaxial growth direction of NWs can be steered by seed crystal morphology. Octahedral seeds grow into inclined NWs possessing six growth directions, whereas half‐octahedral seeds grow into vertical and horizontal NWs. Interfacial energies between the seed material and the substrate are critical in determining the morphology of seed crystals. We also demonstrate that non‐SERS‐active Pt NWs can show strong surface‐enhanced Raman scattering (SERS) spectra by placing them on Ag films. The active SERS observation would help to elucidate platinum‐catalyzed chemical reactions.     

ZnGa2O4 Nanorod Arrays Decorated with Ag Nanoparticles as Surface‐Enhanced Raman‐Scattering Substrates for Melamine Detection

The availability of sensitive, reproducible, and stable substrates is critically important for surface‐enhanced Raman spectroscopy (SERS)‐based applications, but it presently remains a challenge. In this work, well‐aligned zinc gallate (ZnGa₂O₄) nanorod arrays grown on a Si substrate by chemical vapor deposition were used as templates to fabricate SERS substrates by deposition of Ag nanoparticles onto the ZnGa₂O₄ nanorod surfaces. The coverage of the Ag nanoparticles on the ZnGa₂O₄ nanorod surfaces was easily controlled by varying the amount of AgNO₃. SERS measurements showed that the number density of Ag nanoparticles on the ZnGa₂O₄ nanorod surfaces had a great effect on SERS activity. The SERS signals collected by point‐to‐point and SERS mapping images showed that as‐prepared SERS substrates exhibited good spatial uniformity and reproducibility. Detection of melamine molecules at low concentrations (1.0×10^?7 M ) was used as an example to show the possible application of such a substrate. In addition, the effect of benzoic acid on the detection of melamine was also investigated. It was found that the SERS signal intensity of melamine decreased greatly as the concentration of benzoic acid was increased.     

二步电沉积法制备Au/氧化石墨烯复合薄膜作为SERS基底

采用二步电沉积方法在Ti片表面制备了Au-氧化石墨烯（Au-GO）复合薄膜,通过XRD、SEM、XPS等对薄膜的组成、结构和形貌进行了表征,并以罗丹明6G（R6G）为探针分子,对Au-GO/Ti基底的SERS活性进行了表征。结果显示,Au纳米颗粒尺寸约为60 nm,均匀、致密分布于GO表面,该基底显示出较高的SERS活性,对R6G分子的检测极限可达~10^-10 mol·L^-1,增强因子高达约10⁶,且基底显示出良好的稳定性,在冰箱中存放90 d后,SERS活性仅降低30%左右。     

二步电沉积法制备Au/氧化石墨烯复合薄膜作为SERS基底

采用二步电沉积方法在Ti片表面制备了Au-氧化石墨烯（Au-GO）复合薄膜,通过XRD、SEM、XPS等对薄膜的组成、结构和形貌进行了表征,并以罗丹明6G（R6G）为探针分子,对Au-GO/Ti基底的SERS活性进行了表征。结果显示,Au纳米颗粒尺寸约为60 nm,均匀、致密分布于GO表面,该基底显示出较高的SERS活性,对R6G分子的检测极限可达~10^-10 mol·L^-1,增强因子高达约10⁶,且基底显示出良好的稳定性,在冰箱中存放90 d后,SERS活性仅降低30%左右。     

Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: Origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates

The fabrication of effective surface-enhanced Raman scattering (SERS) substrates has been the subject of intensive research because of their useful applications. In this paper, dendritic gold (Au) rod (DAR) structures prepared by simple one-step electrodeposition in a short time were examined as an effective SERS-active substrate. The SERS activity of the DAR surfaces was compared to that of other nanostructured Au surfaces with different morphologies, and its dependence on the structural variation of DAR structures was examined. These comparisonal investigations revealed that highly faceted sharp edge sites present on the DAR surfaces play a critical role in inducing a high SERS activity. The SERS enhancement factor was estimated to be greater than 10⁵, and the detection limit of rhodamine 6G at DAR surfaces was 10⁻⁸ M. The DAR surfaces exhibit excellent spot-to-spot and substrate-to-substrate SERS enhancement reproducibility, and their long-term stability is very good. It was also demonstrated that the DAR surfaces can be effectively utilized in electrochemical SERS systems, wherein a reversible SERS behavior was obtained during the cycling to cathodic potential regions. Considering the straightforward preparation of DAR substrates and the clean nature of SERS-active Au surfaces prepared in the absence of additives, we expect that DAR surfaces can be used as cost-effective SERS substrates in analytical and electrochemical applications.     

3D aluminum/silver hierarchical nanostructure with large areas of dense hot spots for surface‐enhanced raman scattering

Plasmonic nanomaterials possessing large‐volume, high‐density hot spots with high field enhancement are highly desirable for ultrasensitive surface‐enhanced Raman scattering (SERS) sensing. However, many as‐prepared plasmonic nanomaterials are limited in available dense hot spots and in sample size, which greatly hinder their wide applications in SERS devices. Here, we develop a two‐step physical deposition protocol and successfully fabricate 3D hierarchical nanostructures with highly dense hot spots across a large scale (6 × 6 cm²). The nanopatterned aluminum film was first prepared by thermal evaporation process, which can provide 3D quasi‐periodic cloud‐like nanostructure arrays suitable for noble metal deposition; then a large number of silver nanoparticles with controllable shape and size were decorated onto the alumina layer surfaces by laser molecular beam epitaxy, which can realize large‐area accessible dense hot spots. The optimized 3D‐structured SERS substrate exhibits high‐quality detection performance with excellent reproducibility (13.1 and 17.1%), whose LOD of rhodamine 6G molecules was 10^?9 M. Furthermore, the as‐prepared 3D aluminum/silver SERS substrate was applied in detection of melamine with the concentration down to 10^?7 M and direct detection of melamine in infant formula solution with the concentration as low 10 mg/L. Such method to realize large‐area hierarchical nanostructures can greatly simplify the fabrication procedure for 3D SERS platforms, and should be of technological significance in mass production of SERS‐based sensors.     

有序Au/Ag纳米碗阵列的简易制备及其表面增强拉曼散射性能

通过湿法化学合成基于SiO₂胶体晶体的大面积有序Au/Ag纳米碗(Au/AgNB)阵列。首先,在玻璃基板上组装3D SiO₂胶体晶体作为模板。然后,以Au纳米颗粒(AuNP)为种子,通过原位生长法在SiO₂模板上沉积一层Au纳米壳(AuNS)。再通过HCHO还原Ag⁺成Ag⁰,进一步在AuNS表面沉积Ag纳米壳,形成Ag/Au双纳米壳(Ag/AuNS)阵列。最后通过丙烯酸酯改性双向取向聚丙烯(BOPP)膜方便地获得了单层有序反转Ag/AuNB阵列。这种有序Au/AgNB阵列具有更佳的表面增强拉曼散射(SERS)活性,其SERS分析增强因子(AEF)可达2.23×10⁷。     

有序Au/Ag纳米碗阵列的简易制备及其表面增强拉曼散射性能

通过湿法化学合成基于SiO₂胶体晶体的大面积有序Au/Ag纳米碗(Au/AgNB)阵列。首先,在玻璃基板上以3D SiO₂胶体晶体作为模板。然后,在Au纳米颗粒(AuNP)种子的帮助下,通过原位生长方法在模板上沉积一层Au纳米壳(AuNS)。再通过HCHO还原Ag⁺使AuNS表面进一步沉积Ag纳米壳,形成Ag/Au双纳米壳(Ag/AuNS)阵列。通过丙烯酸酯改性双向取向聚丙烯(BOPP)方便地获得了单层有序反转Ag/AuNB阵列。这种有序Au/AgNB阵列具有更佳的表面增强拉曼散射(SERS)活性,其SERS分析增强因子(AEF)可达2.23×10⁷。     

Dealloying Ag–Al Alloy to Prepare Nanoporous Silver as a Substrate for Surface‐Enhanced Raman Scattering: Effects of Structural Evolution and Surface Modification

Sensitive detection of molecules by using the surface‐enhanced Raman scattering (SERS) technique depends on the nanostructured metallic substrate and many efforts have been devoted to the preparation of SERS substrates with high sensitivity, stability, and reproducibility. Herein, we report on the fabrication of stable monolithic nanoporous silver (NPS) by chemical dealloying of Ag–Al precursor alloys with an emphasis on the effect of structural evolution on SERS signals. It was found that the dealloying conditions had great influence on the morphology (the ligament/pore size) and the crystallization status, which determined the SERS signal of rhodamine 6G on the NPS. NPS with small pores, low residual Al, and perfect crystallization gave high SERS signals. A high enhancement factor of 7.5×10⁵ was observed on bare NPS obtained by dealloying Ag₃₀Al₇₀ in 2.5 wt % HCl at room temperature followed by 15 min aging at around 85 °C. After coating Ag nanoparticles on the NPS surface, the enhancement factor increased to 1.6×10⁸ owing to strong near‐field coupling between the ligaments and nanoparticles.     

Rolling‐Circle Amplification Detection of Thrombin Using Surface‐Enhanced Raman Spectroscopy with Core‐Shell Nanoparticle Probe

An ultrasensitive surface‐enhanced Raman spectroscopy (SERS) sensor based on rolling‐circle amplification (RCA)‐increased “hot‐spot” was developed for the detection of thrombin. The sensor contains a SERS gold nanoparticle@Raman label@SiO₂ core‐shell nanoparticle probe in which the Raman reporter molecules are sandwiched between a gold nanoparticle core and a thin silica shell by a layer‐by‐layer method. Thrombin aptamer sequences were immobilized onto the magnetic beads (MBs) through hybridization with their complementary strand. In the presence of thrombin, the aptamer sequence was released; this allowed the remaining single‐stranded DNA (ssDNA) to act as primer and initiate in situ RCA reaction to produce long ssDNAs. Then, a large number of SERS probes were attached on the long ssDNA templates, causing thousands of SERS probes to be involved in each biomolecular recognition event. This SERS method achieved the detection of thrombin in the range from 1.0×10^?12 to 1.0×10^?8 M and a detection limit of 4.2×10^?13 M , and showed good performance in real serum samples.     

Direct evidence of chemical effect of surface-enhanced Raman scattering observed on electrochemically prepared rough gold substrates

In this study, polypyrrole (PPy) films were electrochemically deposited on gold substrates roughened by an electrochemical triangular-wave oxidation-reduction cycles (ORC) in an aqueous solution containing 0.1N KCl. Then the substrates were heated from 25 to 50 °C and the corresponding SERS performances of PPy were observed in situ. The results indicate that the SERS enhancement capabilities of substrates are gradually raised from 25 °C to a maximum at 40 °C and monotonically decreased from 40 to 50 °C. These SERS enhancement capabilities ascribed to the charge transfers from PPy to Au, which are responsible for the chemical effects of SERS mechanisms, are successfully observed via SERS and high resolution X-ray photoelectron spectroscopy (HRXPS) analyses. The variation in content of the oxidized PPy peak of the double peaks in the range of 1000-1150 cm⁻¹ in SERS spectrum obtained on an Au substrate at different temperatures is consistent with its corresponding variation in the SERS intensity of PPy. The variation in content of the oxidized nitrogen of PPy deposited on an Au substrate at different temperatures revealed from an HRXPS analysis also confirms this consistence.     

Click Chemistry Mediated Functionalization of Vertical Nanowires for Biological Applications

Semiconductor nanowires (NWs) are gaining significant importance in various biological applications, such as biosensing and drug delivery. Efficient and controlled immobilization of biomolecules on the NW surface is crucial for many of these applications. Here, we present for the first time the use of the Cu^I‐catalyzed alkyne–azide cycloaddition and its strain‐promoted variant for the covalent functionalization of vertical NWs with peptides and proteins. The potential of the approach was demonstrated in two complementary applications of measuring enzyme activity and protein binding, which is of general interest for biological studies. The attachment of a peptide substrate provided NW arrays for the detection of protease activity. In addition, green fluorescent protein was immobilized in a site‐specific manner and recognized by antibody binding to demonstrate the proof‐of‐concept for the use of covalently modified NWs for diagnostic purposes using minute amounts of material.     

Sensing of 2,4-dichlorophenoxyacetic acid by surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) spectra of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was obtained by employing a bi-layer gold substrate, assembled by the reduction of Au(III) over gold-seeded nanoparticles immobilized on functionalized glass substrates. The SERS signal was linear with the logarithm of the solution concentrations between 1.0 × 10⁻⁷ mol L⁻¹ and 1.0 × 10⁻³ mol L⁻¹, indicating that the bi-layer gold substrate affords a significant dynamic range for SERS, providing an excellent analytical response within this concentration range, and revealing the high sensitivity of the gold surface towards such analyte. In addition, using the same gold substrate, a similar calibration curve was obtained for crystal-violet (CV), and it was possible to identify the concentration limit corresponding to the transition from the average SERS to the nonlinear SERS response.     

Single-step multiplex detection of toxic metal ions by Au nanowires-on-chip sensor using reporter elimination

We have developed a Au nanowires (NWs)-on-chip surface-enhanced Raman scattering (SERS) multiplex sensor that can sensitively detect multiple toxic metal ions. Most importantly, the reporter elimination method simplified the detection procedure to a single step, which has been much desired for remote environmental monitoring. This sensor has several notable features. First, it shows high reproducibility based on well-defined single-crystalline Au NWs. Second, single-NW-sensors that can detect a specific metal ion are combined for multiplex sensing of metal ions. Third, when a sample solution is put onto the NWs-on-chip sensor, a decrease in the SERS signal of a specific NW-sensor identifies the target metal ion. Simple, rapid, sensitive and quantitative detection of metal ions becomes possible through the measurement of the SERS signals. We successfully detected ions of mercury (Hg(2+)), silver (Ag(+)), and lead (Pb(2+)) coexisting in the same solution by using this sensor.