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.     

Fabrication and applications of ultraflexible nanostructures using dielectric heating-assisted nanoimprint on PVC films

We developed dielectric heating-assisted nanoimprint method for rapid fabrication of ultraflexible nanostructures. Using spin-coating polyvinyl-chloride (PVC) film on the glass slide, the dielectric heating on PVC film helped the pattern transfer from the mold to PVC film in few seconds. Various kinds of nanostructures were successfully made on PVC films with about 20-μm thickness. We demonstrated the applications of ultraflexible metallic nanostructures for bending measurement using surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) on the curved surfaces. For measuring bending angles using SPR on capped nanowire arrays, the minimum detection angle was 2.4 × 10⁻³ degree under 0.02 nm wavelength resolution. For SERS measurement, the nanorod arrays on a curved substrate can increase SERS signals for two times as compared to planar SERS substrate.     

Preparation of large-area surface-enhanced Raman scattering active Ag and Ag/Au nanocomposite films

Ag films on tinning glass substrates were fabricated by modified silver-mirror (Tollen’s) reaction with the advantage of low-cost, simple and quick fabrication process. The obtained Ag films were served as sacrificial materials for preparation of Ag/Au nanocomposite films by immersing in a chlorauric acid (HAuCl₄) solution at room temperature. After a short time of galvanic replacement reaction, Ag/Au bimetallic nanostructures were synthesized with “concave” structures. The morphology, properties and composition of the Ag and Ag/Au nanocomposite films were analyzed by using scanning electron microscopy (SEM), UV-visible spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDS) and surface enhanced Raman scattering (SERS). SEM images displayed that the large area of Ag film and Ag/Au bimetallic nanostructures experienced structural evolution process during galvanic reaction. The UV-Vis spectra showed the absorbencies characterization of Ag film and Ag/Au nanocomposite films. SERS measurements using methylene blue as an analyte showed that SERS intensities of bimetallic films were enhanced significantly compared with that of pure Ag films. The SERS enhancement ability of Ag/Au bimetallic films was dependent on the immersion time for galvanic replacement reaction.     

Au/TiN复合薄膜制备及其表面增强拉曼光谱研究

表面增强拉曼散射光谱(SERS)已用于环境监测、生物医药、食品卫生等领域,而高活性SERS基底是表面增强拉曼散射光谱技术应用的关键。TiN作为新型等离子材料具有较强的SERS性能,同时化学稳定性及生物相容性较好,但其SERS性能不如贵金属金强。该研究采用氨气还原氮化法和电化学沉积法,在TiN薄膜表面沉积贵金属Au纳米颗粒制备出Au/TiN复合薄膜。在Au/TiN复合薄膜中单质Au和TiN两种物相共存;随着电化学沉积时间延长,TiN薄膜表面单质金纳米颗粒数量逐渐增多,金纳米颗粒尺寸增大,颗粒间距减小。由于金与TiN两者的本征表面等离子共振耦合作用,Au/TiN复合薄膜的共振吸收峰发生了偏移。利用罗丹明6G为拉曼探针分子,对Au/TiN复合薄膜进行SERS性能分析,发现Au/TiN复合薄膜上的R6G探针分子的拉曼峰信号强度随沉积时间延长呈现先增大后减小的规律;当电化学沉积时间为5 min时,R6G拉曼信号峰较高,复合薄膜样品的SERS活性最大。将Au/TiN复合薄膜和Au薄膜分别浸泡在10-3,10-5,10-7,10-8及10-9 mol·L-1 R6G溶液5 min,进行检测限分析,发现Au/TiN复合薄膜检测极限达10-8 mol·L-1,增强因子达到8.82×105,与Au薄膜和TiN薄膜相比,Au/TiN复合薄膜上对R6G探针分子SERS活性最高。这得益于Au/TiN复合膜中表面等离子体产生的耦合效应,使得局域电磁场强度增强,从而引起R6G探针分子拉曼信号增强。通过2D-FDTD模拟电场分布发现Au/TiN,Au及TiN薄膜具有电场增强作用,其中Au/TiN复合薄膜的增强作用尤为显著,这也证实了氮化钛与金纳米颗粒之间存在耦合效应。另外发现TiN与Au之间可能存在电荷转移,促进了4-氨基苯硫酚氧化反应,进而证实了TiN与Au薄膜的协同作用。此外,Au/TiN复合薄膜均匀性较好,相对平均偏差仅为7.58%。由此可见,采用电化学沉积制备的Au/TiN复合薄膜具有作为SERS基底材料的应用潜力。     

Multiscale electromagnetic SERS enhancement on self‐assembled micropatterned gold nanoparticle films

In this work, we demonstrate a cascaded, multiplicative electromagnetic enhancement effect in surface‐enhanced Raman scattering (SERS) on periodically micropatterned films made of colloidal gold nanoparticles, prepared by a self‐assembly approach, without implying lithography procedures. The multiplicative enhancement effect is obtained by combining surface plasmon near‐field enhancement due to nanoscale features with far‐field photonic coupling by periodic microscale features. The effect is observed for both internal Raman reporters (molecules attached to the Au colloids before their assembly) and external Raman probes (molecules adsorbed on the samples after film assembly). The ability of the patterned films for far‐field light coupling is supported by reflectivity spectra, which present minima/maxima in the visible spectral range. Finite‐difference time‐domain computer simulations of the electric field distribution also support this interpretation. The fabricated dual‐scale SERS substrates exhibit a good spot‐to‐spot reproducibility and time stability, as proved by the SERS response over a time scale longer than 1 month. The experimental demonstration of this cascaded electromagnetic enhancement effect contributes to a better understanding of SERS and can affect future design of SERS substrates. Moreover, such dual‐scale colloidal films prepared by convective self‐assembly can be of general interest for the broader field of nanoparticle‐based devices. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation of monodisperse bimetallic nanorods with gold nanorod core and silver shell and their plasmonic property and SERS efficiency

In this study, monodisperse bimetallic nanorods with gold (Au) nanorod core and silver (Ag) shell (Au@AgNRs) were synthesized through seed‐mediated growth process by reduction of AgNO₃ using Au nanorods with narrow size and shape distribution as seeds. With increasing the used amount of AgNO₃, the Ag shell thickness of their lateral facets is raised faster than that of their two tips, leading to a decrease of their aspect ratios. Four plasmon bands are observable on the extinction spectra of Au@AgNRs, which are attributed to the longitudinal dipolar plasmon mode, transverse dipolar plasmon mode, and octupolar plasmon mode of the core‐shell structured bimetallic nanorods, respectively. As their Ag shell thickness increases, their longitudinal plasmon band blue‐shifts notably with the transverse plasmon band blue‐shifting and the two octupolar plasmon bands red‐shifting slightly, due to the decrease of their aspect ratios and enhancement of Ag plasmon resonance contribution. When used as surface‐enhanced Raman scattering (SERS) substrate for probing minute amounts of 4‐mercaptobenzoic acid in aqueous solution, Au@AgNRs have much stronger SERS activity than Au nanorods, and the obtained Raman signals are highly reproducible arising from their excellent monodispersity. Their SERS activity is remarkably increased with their Ag shell thickness thanks to the enhancing surface electric field and the chemical enhancement associated with electronic ligand effect. Copyright © 2014 John Wiley & Sons, Ltd.     

A facile high‐performance SERS substrate based on broadband near‐perfect optical absorption

Plasmonic systems based on metal nanoparticles on a metal film with high optical absorption have generated great interests for surface‐enhanced Raman scattering (SERS). In this study, we prepare a broadband‐visible light absorber consisting Au nanotriangles on the surface of a continuous optically opaque gold film separated with a dielectric SiO₂ layer, which is a typical metal‐insulator‐metal (MIM) system, and demonstrate it as an efficient SERS substrate. The MIM nanostructure, prepared using nanosphere lithography with a very large area, shows a broadband with absorption exceeding 90% in the wavelength regime of 630–920 nm. We observe an average SERS enhancement factor (EF) as large as 4.9 × 10⁶ with a 22‐fold increase compared to a single layer of Au nanotriangles directly on a quartz substrate. A maximum SERS EF can be achieved by optimizing the thicknesses of the dielectric layer to control the optical absorption. Owing to the simple, productive, and inexpensive fabrication technique, our MIM nanostructure could be a potential candidate for SERS applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhancement in SERS intensity with hierarchical nanostructures by bimetallic deposition approach

We investigate the plasmonic enhancement arising from bimetallic (Au/Ag) hierarchical structure and address the fundamental issues relating to the design of multilayered nanostructures for surface‐enhanced Raman scattering (SERS) spectroscopy. SERS‐active nanosphere arrays with Ag underlayer and Au overlayer were systematically constructed, with the thickness of each layer altered from 40 to 320 nm. The SERS responses of the resultant bimetallic structures were measured with 2‐naphthalenethiol dye as the test sample. The results confirm the dependency of SERS enhancement on the thickness ratio (Au : Ag). Compared with Au‐arrays, our optimized bimetallic structures, which exhibit nanoprotrusions on the nanospheres, were found to be 2.5 times more SERS enhancing, approaching the enhancement factor of an Ag‐array. The elevated SERS is attributed to the formation of effective hot‐spots associated with increased roughness of the outer Au film, resulting from subsequent sputtering of Au granules on a roughened Ag surface. The morphology and reflectance studies suggest that the SERS hot‐spots are distributed at the junctions of interconnected nanospheres and over the nanosphere surface, depending on the thickness ratio between the Au and Ag layers. We show that, by varying the thickness ratio, it is possible to optimize the SERS enhancement factor without significantly altering the operating plasmon resonance wavelength, which is dictated solely by the size of the underlying nanospheres template. In addition, our bimetallic substrates show long‐term stability compared with previously reported Ag‐arrays, whose SERS efficiency drops by 60% within a week because of oxidation. These findings demonstrate the potential of using such a bimetallic configuration to morphologically optimize any SERS substrate for sensing applications that demand huge SERS enhancement and adequate chemical stability. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

金纳米颗粒阵列基底的化学置换制备及其表面增强拉曼散射特性研究

表面增强拉曼(SERS)作为一种分析手段,具有高灵敏度、高选择性、高重复性、非破坏性等优点,在过去的几十年中,被广泛应用在成分检测、环境科学、生物医药及传感器等领域。其中以金、银等贵金属纳米颗粒薄膜在表面增强拉曼(SERS)活性基底方面得到了更为广泛的应用。SERS技术一个关键的因素是如何制设计并备具有大面积、高增强能力及高重复性、可循环使用的SERS基底。通常,贵金属纳米颗粒规则阵列结构的单元颗粒电磁增强特性及其颗粒间的电磁耦合增强特性的综合作用可大力提升SERS基底的探测性能。然而,利用传统微纳米加工方法如光刻、电子束光刻等方法制备得到的贵金属纳米阵列结构的表面粗糙度不够理想。结合光刻与化学置换方法制备金纳米颗粒四方点阵列孔洞结构,并研究其作为SERS基底的电磁增强特性。具体研究利用光刻法在硅衬底上制备了规则排列的四方点阵列孔洞结构,用磁控溅射在其表面镀上金属铁膜;接着在衬底上旋涂浓度为1.893 8 mol·L-1的氯金酸液膜,在孔洞内铁和氯金酸发生置换反应,进而孔洞生成金纳米颗粒,最终得到金纳米颗粒四方点阵SERS活性基底。采用罗丹明6G(R6G)分子作为探测分子测试不同金纳米颗粒阵列结构基底的SERS谱。实验结果表明,随着化学置换反应时间的延长,金纳米颗粒排列更加紧凑有序,SERS谱增强性能更好。     

Spectral characterization and intracellular detection of Surface‐Enhanced Raman Scattering (SERS)‐encoded plasmonic gold nanostars

Plasmonic gold nanostars offer a new platform for surface‐enhanced Raman scattering (SERS). However, due to the presence of organic surfactant on the nanoparticles, SERS characterization and application of nanostar ensembles in solution have been challenging. Here, we applied our newly developed surfactant‐free nanostars for SERS characterization and application. The SERS enhancement factors (EF) of silver spheres, gold spheres and nanostars of similar sizes and concentration were compared. Under 785 nm excitation, nanostars and silver spheres have similar EF, and both are much stronger than gold spheres. Having plasmon matching the incident energy and multiple ‘hot spots’ on the branches bring forth strong SERS response without the need to aggregate. Intracellular detection of silica‐coated SERS‐encoded nanostars was also demonstrated in breast cancer cells. The non‐aggregated field enhancement makes the gold nanostar ensemble a promising agent for SERS bioapplications. Copyright © 2012 John Wiley & Sons, Ltd.     

Regular Hexagonal Gold Nanoprisms Fabricated by a Physical Method: Toward Use as Ultrasensitive Surface‐Enhanced Raman Scattering Substrates

A simple physical approach to prepare gold (Au) nanoparticles with sharp edges for increasing surface‐enhanced Raman scattering (SERS) response is presented. The shape evolution process of Au nanoparticles under different fabrication conditions is studied, and a thermodynamic model is adopted to explain the shape transition. Single‐crystalline Au nanoprisms with regular hexagonal shape can be formed at a certain annealing temperature. Coating of these Au nanoprisms with graphene causes them to exhibit a SERS enhancement of 60x. This is the first demonstration of a physical approach to fabricate regular hexagonal Au nanoprisms that exhibit an ultrasensitive SERS effect. Furthermore, the local field distribution of a series of Au nanoprisms with different sizes is simulated to better understand their ultrasensitive SERS performance.     

Nanostructured Au/Si substrate for organic molecule SERS detection

Nanoparticles of noble metals, such as gold and silver, exhibit unique and tunable optical properties on account of their surface plasmon resonance. In particular, gold nanoparticles on silicon substrates are attractive for future nanoscale sensors and optical devices due to their resistance to oxidation and due to their electrical and optical properties. In this study, we developed a nanostructured gold/macroporous silicon (Au/PS) substrate capped with 11-mercaptoundecanoic acid (11-MUA) with ultra-sensitive detection properties achieved in characterization, an approach based on surface-enhanced Raman scattering (SERS). Surface-enhanced Raman scattering allows us to detect substances at a low concentration level and to observe structural details of a thiol molecule bonded to small film thicknesses. Raman measurements were carried out at 514 nm and 785 nm. In order to emphasize the effect of the Si microstructuration on the efficiency of this new substrate (Au/PS) proposed for SERS experiments, the same molecule (11-MUA) was adsorbed on it as well as on gold/atomically flat silicon (Au/Si) and on commercial Klarite (Mesophotonics) substrates. Systematic studies realized by Raman spectroscopy, electron microscopy, and X-ray spectroscopy show the influence of silicon substrate texturing and metallic deposition conditions, including time and temperature on the optical phenomena.     

Rapid Preparation of Large-Area Densely Packed Plasmonic Hot-Spots for Reliable Sers Sensing

A facile, efficient and time-saving strategy is proposed to obtain large-area and reliable surface-enhanced Raman scattering (SERS) substrates via artificial heat-treatment of Au nanoparticles or ultrathin Au films sputtered on the silica substrates. Excellent Raman enhancements with the detection limitation down to 10^–9 mol/L are obtained due to the highly-dense plasmonic hot-spots and strong plasmons near-field coupling. Decreased intensity of Raman peaks with the increased sputtering time of Au nanoparticles or ultrathin films mainly originates from the excited and hybridized coupling of multiple surface plasmons. The simple fabrication strategy and superior performance make these substrates promising candidates for the development of inexpensive and reliable SERS substrates.

     

SERS detection of polychlorinated biphenyls using β‐cyclodextrin functionalized gold nanoparticles on agriculture land soil

A highly sensitive surface‐enhanced Raman scattering (SERS) platform for the selective trace analysis of persistent organic pollutant (POP) such as polychlorinated biphenyl (PCBs) was reported based on β‐CD modified gold nanoparticles (AuNPs) with the real environmental sample of polluted soil. The synthesized gold nanoparticles were characterized using UV–vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) and transmission electron microscopy (TEM). In polluted soil the presentation of PCB is confirmed by using GC‐MS. It is further verified and confirmed by using SERS. When the contaminated soil was added to the system, the binding of soil with β‐CD resulted in the aggregation of AuNPs, and excellent Raman signal was obtained which can reflect the isomers of polychlorinated biphenyls. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering sensing on black silicon

Reactive ion etching was used to fabricate black‐Si over the entire surface area of 4‐inch Si wafers. After 20 min of the plasma treatment, surface reflection well below 2% was achieved over the 300–1000 nm spectral range. The spikes of the black‐Si substrates were coated by gold, resulting in an island film for surface‐enhanced Raman scattering (SERS) sensing. A detection limit of 1 × 10^?6 M (at count rate > 10² s^?1 . mW^?1) was achieved for rhodamine 6G in aqueous solution when drop cast onto a ～ 100‐nm‐thick Au coating. The sensitivity increases for thicker coatings. A mixed mobile‐on‐immobile platform for SERS sensing is introduced by using dog‐bone Au nanoparticles on the Au/black‐Si substrate. The SERS intensity shows a non‐linear dependence on the solid angle (numerical aperture of excitation/collection optics) for a thick gold coating that exhibits a 10 times higher enhancement. This shows promise for augmented sensitivity in SERS applications.     

Trace analysis of polycyclic aromatic hydrocarbons using calixarene layered gold colloid film as substrates for surface‐enhanced Raman scattering

A surface‐enhanced Raman scattering (SERS) active substrate for the detection of polycyclic aromatic hydrocarbons (PAHs) was developed, which used 25, 27‐dimercaptoacetic acid‐26, 28‐dihydroxy‐4‐terbutyl calix[4]arene (DMCX) to functionalize a gold colloid film. This SERS‐active substrate prepared by self‐assembly method exhibits a high sensitivity, especially for the detection of PAHs. With the use of this SERS‐active substrate and with the application of the shifted excitation Raman difference spectroscopy (SERDS) technique, Raman signals of pyrene and anthracene in aqueous solutions at low concentration level (500 pM) can be obtained. Moreover, because PAHs are blocked from being directly adsorbed on gold colloid by DMCX and the photochemical reactions of adsorbates are avoided, the Raman bands of PAHs adsorbed on DMCX‐fuctionalized gold colloid film can be one‐to‐one correspondence with those of solid PAHs, and additionally, this SERS‐active substrate can be easily cleaned and reused. The obtained results demonstrate that the DMCX‐functionalized gold colloid films prepared by self‐assembly method have great potential to be developed to an in situ PAHs detection substrate. Copyright © 2012 John Wiley & Sons, Ltd.     

Modeling of regular gold nanostructures arrays for SERS applications using a 3D FDTD method

We study the localized surface plasmon resonance (LSPR) and the surface-enhanced Raman scattering (SERS) of arrays of gold cylindrical and ellipsoidal nanoparticles with different diameters or major axes. The LSPR and SERS gains are calculated with the three dimensional Finite-Difference Time-Domain method using the Drude–Lorentz dispersion model. We find that the maximum of the extinction spectrum and the average SERS gain of each investigated nanostructures are shifted whatever their size and their shape. PACS 42.25.Fx; 71.45.Gm; 78.30.-j     

Steric hindrance in cationic and neutral rhodamine 6 G molecules adsorbed on Au nanoparticles

The adsorption of cationic and neutral R6G molecules on Au nanoparticles was elucidated by surface enhanced Raman scattering (SERS). The steric hindrance at hydroethyl amino (‐N(H)Et) groups in R6G was evidenced by the observation that R6G⁺ adsorb on as‐prepared gold nanoparticles (AuNPs) only with electrostatic forces, in contrast to the electrostatic and chemical adsorption of R123⁺ with dihydro amino (‐NH₂) groups on as‐prepared AuNPs. Large steric hindrance at the amino groups in R6G yielded saturated coverage of 700 molecules/AuNP for R6G⁺ significantly fewer than 1000 molecules/AuNP for R123⁺. In addition, neutral R6G⁰ on AuNPs showed markedly enhanced peaks at 1200–1600 cm⁻¹, which were not observed in Raman spectra of R6G⁰ in bulk solution, and also in SERS of R6G⁺ on AuNPs. These bands are attributed to vibrational modes of an outer phenyl ring and ethyl amino groups, which are vertical to a xanthene plane, on the basis of theoretical analysis of molecular vibrations. Thus, Raman scattering of these bands is enhanced under an inclined orientation of R6G⁰ molecules chemisorbed on AuNPs via lone pair electrons at amino groups. Copyright © 2013 John Wiley & Sons, Ltd.     

Optimization of extinction efficiency of gold‐coated polystyrene bead substrates improves surface‐enhanced Raman scattering effects by post‐growth microwave heating treatment

We report a novel post‐growth microwave treatment approach to selectively modify the surface morphologies of gold (Au) films coated on the polystyrene (PS) bead substrates for effectively improving the surface‐enhanced Raman scattering (SERS) effect on the analytes. The discrete dipole approximation (DDA) model was introduced to evaluate the enhancement effects by calculating the localized electromagnetic field distribution and extinction efficiency based on the sizes of the trenches and voids, and the surface roughness of the modified Au–PS bead substrates. The SERS performance of microwave‐modified Au–PS substrates on rhodamine 6G (Rh 6G) and saliva yields at least 10‐fold improvements in SERS intensities compared to the as‐grown substrates, which is also in agreement with theoretical predictions by DDA modeling. This work demonstrates both experimentally and theoretically the efficacy of the microwave heating treatment on modifying the Au–PS bead substrates for the realization of high SERS performance in biomedical applications. Copyright © 2009 John Wiley & Sons, Ltd.