Preparation of silver nanoparticles on zinc oxide nanowires by photocatalytic reduction for use in surface‐enhanced Raman scattering measurements

To increase the sensitivity in surface‐enhanced Raman scattering (SERS) measurements, the high surface area of zinc oxide nanowires (ZnO NWs) was used. ZnO NWs on silicon substrates were prepared and used as substrates for further growth of silver nanoparticles (AgNPs). Ultraviolet (UV) irradiation was used to reduce silver ions to AgNPs on the ZnO wires. With proper growth conditions for both ZnO NWs and AgNPs, the substrates exhibit SERS enhancement factors greater than 10⁶. To understand the influences of the morphologies of the ZnO NWs on the growth of AgNPs, the growing time and temperature were varied. The concentration of silver nitrate and irradiation time of UV radiation were also varied. The resulting AgNPs were probed with para‐nitrothiophenol to quantify the SERS enhancements obtained from the varying conditions. The results indicate that ZnO NWs could be grown at temperatures higher than 490 °C and higher growth temperatures result in smaller diameter of the formed ZnO NWs. Also, the morphologies of ZnO NWs did not significantly alter the SERS signals. The concentration of silver nitrate affects the SERS signals significantly and the optimal concentration was found to be in the range of 10–20 mM. With irradiation times longer than 90 s, the resulting AgNPs showed similar SERS intensities. With optimized conditions, the AgNPs/ZnO substrates are highly suitable for SERS measurements with a typical enhancement factor of higher than 10⁶. Copyright © 2010 John Wiley & Sons, Ltd.     

Photochemical decoration of silver nanoparticles on ZnO nanowires as a three‐dimensional substrate for surface‐enhanced Raman scattering measurement

To increase the sensitivity in surface‐enhanced Raman scattering (SERS) measurement, a three‐dimensional (3D) SERS substrate was prepared by the decoration of silver nanoparticles (AgNPs) on the side walls of ZnO nanowires. The prepared 3D SERS substrates provide the advantages of highly loaded density of AgNPs, with a large specific surface area to interact with analytes, and the ease for the analytes to access the surfaces of AgNPs. To prepare the substrates, ZnO nanowires were first grown on a glass plate by wet chemical method. By treating SnCl₂ on the surfaces of ZnO nanowires, Ag seeds could be formed on the side wall of the ZnO nanowires, which were further grown to a suitable size for SERS measurements via photochemical reduction. To optimize and understand the influences of the parameters used in preparation of the substrates, the reaction conditions were systematically adjusted and examined. Results indicated that AgNPs could be successfully decorated on the side wall of the ZnO nanowires only by the assistances of SnCl₂. The size and density of AgNPs were affected by both the concentration of silver nitrate and the irradiation time. With optimized condition, the prepared 3D substrates provided an enhancement factor approaching 7 orders of magnitude compared with conventional Raman intensity. Copyright © 2014 John Wiley & Sons, Ltd.     

A comparative study of surface‐enhanced Raman scattering from silver‐coated anodic aluminum oxide and porous silicon

Three types of Ag‐coated arrays from porous anodic aluminum oxide (AAO) were prepared and studied as substrates for surface‐enhanced Raman scattering (SERS). They were compared with Ag‐coated porous silicon (PSi) samples. AAO‐based substrates were prepared by the vapor deposition of silver directly onto the surface of porous AAO with different morphologies of the pores, whereas SERS‐active island films on the PSi were prepared by immersion plating. The resulting metallic nanostructures were characterized by UV‐vis absorption spectroscopy and scanning electron microscopy (SEM). Thermal evaporation leads to the formation of granular arrays of Ag nanoparticles on the surface of AAO. SERS activity of the substrates was tested using water‐soluble cationic Zn(II)‐tetrakis (4‐N‐methylpyridyl) porphyrin (ZnTMPyP4) as a probe molecule. The results indicate that all AAO‐based substrates studied here exhibit some degree of SERS activity. Noteworthy, for excitation at 532 nm, signals from AAO‐based substrates were comparable with those from the PSi‐based ones, whereas for 441.6 nm excitation they were about twice higher. The strongest SERS‐enhancement at 441.6 nm excitationwas provided by the AAO substrates with silver deposited on the monolith (originally nonporous) side of AAO. Preferential SERS‐enhancement of the bands ascribed to the vibrations of the N‐methylpyridinium group of ZnTMPyP4 when going to blue excitation was found. Copyright © 2010 John Wiley & Sons, Ltd.     

Characterization and optimization of AuNPs labeled by Raman reporters on glass based on silver enhancement

In this report, gold nanoparticles (AuNPs) labeled by Raman reporters (AuNPs‐R6G) were assembled on glass and used as the seeds to in situ grow silver‐coated nanostructures based on silver enhancer solution, forming the nanostructures of AuNPs‐R6G@Ag, which were characterized by scanning electron microscopy (SEM) and UV‐visible spectroscopy. More importantly, the obtained silver‐coated nanostructures can be used as a surface enhancement Raman scattering (SERS) substrate. The different SERS activities can be controlled by the silver deposition time and assembly time of AuNPs‐R6G on glass. The results indicate that the maximum SERS activity could be obtained on AuNPs‐R6G when these nanostructures were assembled on glass for 2 h with silver deposition for 2 min. In addition, the reproducibility of SERS signal on the fabricated nanostructures is very high with the intensity error lower than 15%, which has great promise as a probe for application in bioanalysis. Copyright © 2008 John Wiley & Sons, Ltd.     

In situ nucleation and growth of silver nanoparticles in membrane materials: a controllable roughened SERS substrate with high reproducibility

A controllable roughened silver surface with high surface‐enhanced Raman scattering (SERS) activity and high reproducibility has been developed in this study. This silver surface was prepared by silver nucleation in polyelectrolyte multilayers (PEMs) and silver‐enlarged growth. First, the small Ag nuclei were synthesized by NaBH₄ in situ reduction of Ag ions on a surface of PEMs. Then the small Ag nuclei formed were effectively enlarged by using a mixture of commercially available reagents named Li Silver . The optical properties and morphologies of the silver substrates have been investigated by ultraviolet–visible (UV–vis) spectroscopy and atomic force microscopy (AFM). The UV–vis and AFM results revealed that the small Ag nuclei separately appeared on the PEMs after NaBH₄ in situ reduction. The size of the enlarged Ag nanoparticles can be easily controlled with the immersing cycle in Li Silver. 4‐Mercaptopyridine (4‐MPY) and Rhodamine 6G (R6G) have been used as Raman probes to evaluate the properties of the new SERS substrates. It has been found that the enhancement factor of R6G reached ∼10⁹ after treatment in Li Silver. Reproducibility has been investigated using the SERS signal intensity at 1094 cm⁻¹ of 4‐MPY. Signals collected over multiple spots within the same substrate resulted in a relative standard deviation (RSD) of 6.38%, while an RSD of 10.33% was measured in signals collected from different substrates. Copyright © 2008 John Wiley & Sons, Ltd.     

Improved performance of surface‐enhanced Raman scattering on silver substrates prepared in nitric acid solutions

In this work, we propose a new electrochemical method to prepare surface‐enhanced Raman scattering (SERS)‐active silver substrates in nitric acid solutions. Experimental results indicate that the SERS intensity of adsorbed Rhodamine 6G (R6G) can be significantly increased, as compared with that of R6G adsorbed on a SERS‐active Ag substrate prepared by an electrochemical method in a chloride‐containing solution, which was generally employed in the literature. Moreover, the SERS of R6G on the newly developed substrate (prepared in a nitric acid solution) still performs well at a high temperature of 250 °C. However, the enhancement capability of the SERS‐active substrate prepared in a chloride‐containing solution is seriously destroyed at temperatures higher than 150 °C. Further investigations indicate that the oxidation states of roughened Ag substrates prepared in nitric acid solutions under different experiment conditions have less influence on the corresponding SERS performances. Instead, different surface morphologies of roughened Ag substrates and different contents of nitrogen‐containing dopping ions on the roughened Ag substrates demonstrate significant effects on the corresponding SERS performances. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanoporous Ag–GaN thin films prepared by metal‐assisted electroless etching and deposition as three‐dimensional substrates for surface‐enhanced Raman scattering

Three‐dimensional (3D) nanoporous gallium nitride (PGaN) scaffolds are fabricated by Pt‐assisted electroless hydrofluoric acid (HF) etching of crystalline GaN followed by in situ electroless deposition of Ag nanostructures onto the interior surfaces of the nanopores, yielding a large surface area substrate for surface‐enhanced Raman scattering (SERS). The resulting 3D SERS‐active substrates have been optimized by varying reaction parameters and starting material concentration, exhibiting enhanced Raman signals 10–100× more intense than either (1) sputtered Ag‐coated porous GaN or (2) Ag‐coated planar GaN. The increase in SERS signal is attributed to a combination of the large surface area and the inherent transparency of PGaN in the visible spectral region. Overall, Ag‐decorated PGaN is a promising platform for high sensitivity SERS detection and chemical analysis, particularly for reaction and metabolic products that can be trapped inside the highly anisotropic nanoscale pores of PGaN. The potential of this sampling mode is illustrated by the ability to acquire Raman spectra of adenine down to 5 fmol. Additionally, correlated SERS and laser desorption/ionization mass spectrometry spectra can be acquired from same sample spot without further preparation, opening new possibilities for the investigation of surface‐bound molecules with substantially enhanced information content. Copyright © 2012 John Wiley & Sons, Ltd.     

Use of atomic layer deposition to improve the stability of silver substrates for in situ,high‐temperature SERS measurements

A method to stabilize silver surface‐enhanced Raman spectroscopy (SERS) substrates for in situ, high‐temperature applications is demonstrated. Silver island films grown by thermal evaporation were coated with a thin layer (from 2.5 to 5 nm) of alumina by atomic layer deposition (ALD), which protects and stabilizes the SERS‐active substrate without eliminating the Raman enhancement. The temporal stability of the alumina‐coated silver island films was examined by measurement of the Raman intensity of rhodamine 6G molecules deposited onto bare and alumina‐coated silver substrates over the course of 34 days. The coated substrates showed almost no change in SERS enhancement, while the uncoated substrates exhibited a significant decrease in Raman intensity. To demonstrate the feasibility of the alumina‐coated silver substrate as a probe of adsorbates and reactions at elevated temperatures, an in situ SERS measurement of calcium nitrate tetrahydrate on bare and alumina‐coated silver was performed at temperatures ranging from 25 to 400 °C. ALD deposition of an ultrathin alumina layer significantly improved the thermal stability of the SERS substrate, thus enabling in situ detection of the dehydration of the calcium nitrate tetrahydrate at an elevated temperature. Despite some loss of Raman signal, the coated substrate exhibited greater thermal stability compared to the uncoated substrate. These experiments show that ALD can be used to synthesize stable SERS substrates capable of measuring adsorbates and processes at high temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Highly efficient silver particle layers on glass substrate synthesized by the sonochemical method for surface enhanced Raman spectroscopy purposes

A fast method for preparing of silver particle layers on glass substrates with high application potential for using in surface enhanced Raman spectroscopy (SERS) is introduced. Silver particle layers deposited on glass cover slips were generated in one-step process by reduction of silver nitrate using several reducing agents (ethylene glycol, glycerol, maltose, lactose and glucose) under ultrasonic irradiation. This technique allows the formation of homogeneous layers of silver particles with sizes from 80 nm up to several hundred nanometers depending on the nature of the used reducing agent. Additionally, the presented method is not susceptible to impurities on the substrate surface and it does not need any additives to capture or stabilize the silver particles on the glass surface. The characteristics of prepared silver layers on glass substrate by the above mentioned sonochemical approach was compared with chemically prepared ones. The prepared layers were tested as substrates for SERS using adenine as a model analyte. The factor of Raman signal enhancement reached up to 5·10⁵. On the contrary, the chemically prepared silver layers does not exhibit almost any pronounced Raman signal enhancement. Presented sonochemical approach for preparation of silver particle layers is fast, simple, robust, and is better suited for reproducible fabrication functional SERS substrates than chemical one.     

High–Yield Production of Uniform Gold Nanoparticles with Sizes from 31 to 577 nm via One‐Pot Seeded Growth and Size‐Dependent SERS Property

In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl₄ into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl₄ solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.     

化学淀积银膜上卤素电解质对吡啶的表面增强喇曼散射(SERS)的影响

本文是载玻片上化学沉淀1000左右粗糙度的银膜,对其吡啶/KX/H_2O 体系(x=F~-,Cl~-,Br~-,I~-)的 SERS 光谱进行了实验研究。分析了不同的卤素电解质,其SERS 光谱峰值大小、位移及吸附态的变化。实验表明:适当的卤素电解质和吡啶的共吸附是产生 SERS 的必要条件。     

Electroless deposition of silver on synthesized calcite via surface modification

Metallic silver was deposited on the surface of synthesized calcite via a simple electroless deposition method. Calcite with cubic morphology was prepared first by homogeneous precipitation and it was subsequently surface modified using ammonium oxalate. The electroless deposition was carried out using formaldehyde as the reducing agent and silver nitrate as the silver source. Both calcite and the silver deposited calcite were characterized by different techniques. Surface modification of calcite with ammonium oxalate is necessary for the deposition of silver and the size of the deposited silver particles could be controlled by changing the deposition parameters such as concentration of the reagents and the deposition time. Lower concentration of silver ions (e.g. 0.01 M AgNO₃) and shorter deposition times (e.g. 30 min) lead to the formation of silver nanoparticles on calcite.     

Controlling the properties of silver nanoparticles deposited on surfaces using supercritical carbon dioxide for surface-enhanced Raman spectroscopy

Silver nanoparticles (AgNPs) have been deposited on silicon and glass surfaces via a supercritical carbon dioxide (sc-CO₂) synthesis route for application in surface-enhanced Raman spectroscopy (SERS). Arrhenius plots revealed that nucleation and growth processes in this system depend on both temperature and surface chemistry. Results also demonstrated that temperature and surface chemistry could be varied to control nanoparticle properties, such as the mean nanoparticle size, density, and surface coverage, providing two useful variables for manipulating the properties of AgNPs deposited on surfaces in this system. These data also provide scientific insight into the underlying mechanisms governing heterogeneous AgNP deposition on a substrate in a sc-CO₂ system in addition to engineering insight into the variables that can be used to manipulate AgNP characteristics. The mean particle size could be tuned over the range 20–200 nm, the interparticle distance could be tuned over the range 70 nm–1 μm, and the surface coverage could be tuned over the range 0.035–0.58. Products were analyzed by scanning electron microscopy with image analysis, transmission electron microscopy, X-ray diffraction, and SERS. The silver nanoparticle-coated substrates were successfully applied in SERS, detecting the model analyte Rhodamine 6G at a concentration of 1 μM, a three orders of magnitude improvement over SERS surfaces previously fabricated in sc-CO₂ systems. Such surfaces can find use in trace concentration analyte detection in biomedical, chemical, and environmental applications.     

Characterization of copper SERS-active substrates prepared by electrochemical deposition

Surface Enhanced Raman Scattering (SERS) on copper substrates of various morphologies, prepared by electrochemical deposition on platinum targets, was investigated. The substrate preparation procedures differed by the coating bath compositions, applied current densities and the duration of individual steps. The surface morphology of the substrates was visualized by means of Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). SERS spectra of selected organic thiols were measured and the relation between SERS spectral intensity and the surface structure of SERS-active substrates was studied. It has been shown that good Raman surface enhancement can be achieved on the copper substrates prepared by electrochemical deposition from ammoniac baths. Copper substrates fabricated from acidic baths did not show efficient Raman surface enhancement. The results of microscopic measurements demonstrated that the average surface roughness value does not play a substantial role, whereas the shape of the surface nanostructures is a key parameter.     

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.     

Raman spectral detection and assessment of thin organic layers on metal substrates: systematic approach from substrate preparation to map evaluation

Raman spectral mapping of thin organic layers on metal substrates is an important analytical tool to characterize these systems. Surface‐enhanced Raman scattering (SERS) spectroscopy is a suitable technique for analysis of such layers. Development of new SERS‐active surfaces with repeatable properties and without disturbing adsorbed species is one of the important steps for reliable assessment of the thin organic layers designed. This paper presents new SERS‐active substrates suitable for both macro (millimeter scale) and microscopic (micrometer scale) spectral mapping, which allow easy regeneration for repetitive experiments. Both gold and silver SERS‐active surfaces prepared by electrochemical deposition were tested. Complete map data evaluation utilities were newly designed and applied, using both ordinarily used and newly modified mathematical algorithms and chemometric procedures. Evaluation of data starts with finite impulse response (FIR) filtration algorithms to eliminate spectral interferences in individual spectra. Principal component analysis was used for transformation of multidimensional data to understandable dimensions. Various mathematical/statistical techniques were then used for data visualization as spectral maps and for similarity testing. Copyright © 2008 John Wiley & Sons, Ltd.     

SERS activity and stability of the most frequently used silver colloids

Single‐molecule detection by surface‐enhanced resonance Raman scattering (SERRS) spectroscopy has been demonstrated for a variety of molecules. The detection of single molecules that do not have a resonance contribution, SERS, has been shown in the case of adenine. However, when colloidal particles isolated on planar substrates are used as the enhancing medium, the presence of anomalous signals significantly complicates the analysis of the spectra. Selection of a silver colloid that minimizes these spurious signals should improve the ultra‐sensitive detection of non‐resonant single molecules by SERS. A range of silver colloids, prepared by different methods, were investigated with respect to their activity and stability. Minimal anomalous signals were obtained from hydroxylamine‐reduced silver colloids, which suggests that this colloid will be better for ultra‐sensitive SE(R)RS experiments compared to the more common citrate‐ and borohydride‐reduced silver colloids. Copyright © 2011 John Wiley & Sons, Ltd.     

Glass‐embedded silver nanoparticle patterns by masked ion‐exchange process for surface‐enhanced Raman scattering

Glass‐embedded silver nanoparticle patterns were fabricated by masked silver–sodium ion‐exchange process followed by etching to reveal the particles for surface‐enhanced Raman scattering (SERS). The intensity of the enhanced Raman signal is comparable to that of the fluorescence, and the detection limit of 1 nM for Rhodamine 6G has been achieved. Raman images at different etching depths and corresponding morphological images are compared to find optimal SERS signal. Our results demonstrate that silver nanoparticle patterns embedded in glass can be used as SERS‐active substrates. Nanoparticles can be formed in a glass of high optical quality and have potential to be integrated with optical waveguides for a sensor chip. Copyright © 2010 John Wiley & Sons, Ltd.     

退火法制备石墨烯-银纳米粒子及其增强拉曼实验

针对目前SERS基底上金属颗粒制备过程中存在的分布不均匀、易氧化和稳定性差等缺点,通过热蒸镀和高温退火获得分布均匀的SERS基底;同时结合石墨烯优良的光学性能、化学惰性、荧光猝灭以及本身的SERS增强等优点,制备了稳定的石墨烯-银纳米颗粒（GE/AgNPs）复合结构SERS基底。通过GE/AgNPs复合结构的拉曼光谱稳定性试验证明了石墨烯在GE/AgNPs结构中起到隔绝银纳米颗粒与空气直接接触及催化氧化银脱氧的作用,有利于SERS基底的时间稳定性。(1) 石墨烯、Ag纳米颗粒及其复合结构的制备。首先采用热蒸镀和高温退火的方法使Ag纳米颗粒均匀地沉积在SiO₂/Si基底上,再采用化学气相沉积法在Cu箔上制备少层石墨烯,并用湿法转移法将石墨烯转移到目标基底上,并实验研究了以不同的退火顺序对GE/AgNPs基底造成的影响。(2) 石墨烯、Ag纳米颗粒及其复合基底的表征。分别采用光学显微镜、扫描电子显微镜和拉曼光谱进行表征,得到转移后的纯石墨烯较完整地覆盖在SiO₂/Si基底上面,表面比较平整,但在少数地方仍然存在褶皱和杂质;SEM表征结果表明对于不同制备流程的GE/AgNPs复合结构上的Ag纳米颗粒基本呈球形。基本符合Ostwald熟化理论,通过对退火温度和时间的控制能获得平均粒径在40~60 nm的银颗粒,且分布较均匀。此外,在不同退火顺序中,石墨烯的加入对银纳米颗粒的扩散形成扩散势垒,从而出现较大的不规则的颗粒。(3) 基底稳定性试验和仿真分析。通过基底本身的Raman mapping测试,分析了石墨烯拉曼特征峰峰值和半高宽的变化,得知基底对石墨烯本身的拉曼增强效果主要来源于银纳米颗粒间的电磁场增强。同时采用浓度为10-6 mol·L-1的罗丹明6G (R6G)水溶液作为探针分子,对转移了石墨烯的GE/AgNPs复合基底和未转移石墨烯的Ag纳米颗粒基底进行了SERS稳定性实验。结果表明GE/AgNPs复合基底在1~33 d内衰减较缓慢,30 d后仍能探测到拉曼信号约为原来信号的35.1%~40.6%;而纯Ag基底上随着Ag纳米颗粒在空气中迅速氧化,基底的SERS性能显著下降,在30 d后只有原来信号的5.9%~11.3%。此外,通过实验得到覆盖了石墨烯之后的增强因子约为6.05×105。最后采用时域有限差分算法（FDTD）计算了复合结构的电磁场分布和理论增强因子,其理论增强因子可以达到5.7×105。实验和仿真结果的差异,主要是源于石墨烯的化学增强作用。