SERS activity of Au nanoparticles coated on an array of carbon nanotube nested into silicon nanoporous pillar

A novel composite structure, Au nanoparticles coated on a nest-shaped array of carbon nanotube nested into a silicon nanoporous pillar array (Au/NACNT/Si-NPA), was fabricated for surface-enhanced Raman scattering (SERS). The morphology of the Au/NACNT/Si-NPA composite structure was characterized with the aid of scanning electron microscopy, X-ray diffraction instrumentation and Transmission electron microscopy. Compared with SERS of rhodamine 6G (R6G) adsorbed on SERS-active Au substrate reported, the SERS signals of R6G adsorbed on these gold nanoparticles were obviously improved. This was attributed to the enlarged specific surface area for adsorption of target molecules brought by the nest-shaped CNTs structure.     

一种简单的方法制备SERS基底用于染料分子的富集、降解与检测

用一种简单的方法制备银纳米粒子, 研究了此纳米粒子作为SERS基底、吸附剂和光催化剂的多功能性。在光照条件下研究其对染料分子的光催化性能, 用紫外光谱和表面增强拉曼光谱对整个光催化过程进行动态跟踪检测, 实验结果表明染料分子光照条件下确实被催化降解了。本实验不仅合成了多功能的基底材料, 还赋予了表面增强拉曼光谱新的应用价值, 为光催化实验提供了新的动态跟踪检测方法。     

Facile preparation of Au/Ag bimetallic hollow nanospheres and its application in surface-enhanced Raman scattering

In this paper, an Au/Ag bimetallic hollow nanostructure was obtained by using SiO₂ nanospheres as sacrificial templates. The nanostructure was fabricated via a three steps method. SiO₂@Au nanospheres were first synthesized by the layer-by-layer technique, and then they were coated with a layer of Ag particles, finally, the Au/Ag bimetallic hollow nanospheres were obtained by dissolution of the SiO₂ core by exposure in HF solution. Several characterizations, such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and UV visible absorption spectroscopy were used to investigate the prepared nanostructures. The effectiveness of these Au/Ag bimetallic hollow nanospheres as substrates toward surface-enhanced Raman scattering (SERS) detection was evaluated by using rhodamine 6G (R6G) as a probe molecule. We show that such Au/Ag bimetallic hollow nanospheres structure films which consisting of larger interconnected aggregates are highly desirable as SERS substrates in terms of high Raman intensity enhancement. The Au/Ag bimetallic hollow nanostructured aggregate, interconnected nanostructured aggregate and nanoscale roughness are important factors responsible for this large SERS enhancement ability.     

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。     

银覆盖冠状硅柱阵列基底的制备、SERS特性分析及肿瘤标志物miRNA-106a的检测

以聚苯乙烯(PS)小球为模板,采用金属辅助刻蚀和湿法化学刻蚀技术,制备大面积冠状硅柱阵列,再原位生长银纳米粒子后得到银覆盖冠状硅柱阵列(Ag/Si CPA)基底。实验表明,制备的基底具有优良的表面增强拉曼散射(SERS)特性,电磁增强因子达到1.81×10~6。同时,将制备的罗丹明分子(R6G)标记的DNA发卡探针与基底链接,在与miRNA-106a互补杂交后进行SERS信号检测,获得相应的剂量-响应曲线。结果表明,基于(Ag/Si CPA)基底的SERS特性,开展miRNA-106a的检测,具有特异性好和灵敏度高的优势,检测范围为1 fmol·L~(-1)～100 pmol·L~(-1),检测极限为0.917 fmol·L~(-1)。此外,与实时荧光定量多聚核苷酸链式反应(RT-qPCR)方法相比,不仅检测结果一致,而且基于SERS光谱技术的检测方法具有更高的灵敏度。     

Controllable optical activity of non-spherical Ag and Co SERS substrate with different magnetic field

We experimentally fabricate a non-spherical Ag and Co surface-enhanced Raman scattering(SERS) substrate, which not only retains the metallic plasmon resonant effect, but also possesses the magnetic field controllable characteristics.Raman detections are carried out with the test crystal violet(CV) and rhodamine 6G(R6G) molecules with the initiation of different magnitudes of external magnetic field. Experimental results indicate that our prepared substrate shows a higher SERS activity and magnetic controllability, where non-spherical Ag nanoparticles are driven to aggregate effectively by the magnetized Co and plenty of hot-spots are built around the metallic Ag nanoparticles, thereby leading to the enhancement of local electromagnetic field. Moreover, when the external magnetic field is increased, our prepared substrate demonstrates excellent SERS enhancement. With the 2500 Gs and 3500 Gs(1 Gs = 10~(-4)T) magnetic fields, SERS signal can also be obtained with the detection limit lowering down to 10~(-9)M. These results indicate that our proposed magnetic field controlled substrate enables us to freely achieve the enhanced and controllable SERS effect, which can be widely used in the optical sensing, single molecule detection and bio-medical applications.     

SERS activity of carbon nanotubes modified by silver nanoparticles with different particle sizes

A two-dimensional (2D) surface-enhanced Raman scattering (SERS) substrate is fabricated by decorating carbon nanotube (CNT) films with Ag nanoparticles (AgNPs) in different sizes, via simple and low-cost chemical reduction method and self-assembling method. The change of Raman and SERS activity of carbon nanotubes/Ag nanoparticles (CNTs/AgNPs) composites with varying size of AgNPs are investigated by using rhodamine 6G (R6G) as a probe molecule. Meanwhile, the scattering cross section of AgNPs and the distribution of electric field of CNTs/AgNPs composite are simulated through finite difference time domain (FDTD) method. Surface plasmon resonance (SPR) wavelength is redshifted as the size of AgNPs increases, and the intensity of SERS and electric field increase with AgNPs size increasing. The experiment and simulation results show a Raman scattering enhancement factor (EF) of 10⁸ for the hybrid substrate.     

Hole arrayed metal-insulator-metal structure for surface enhanced Raman scattering by self-assembling polystyrene spheres

A fabrication process based on the self-assembling polystyrene spheres is proposed to obtain hole arrayed metal-insulator-metal （HA-MIM） structure for surface enhanced Raman scattering （SERS）. The localized field enhancement aroused by the gap resonance in the HA-MIM structure is analyzed by finite-different time domain （FDTD） method. With reference to the theory result, the structure is experimentally fabricated and the Raman scattering spectrum of rhodamine 6G （R6G） is measured by a miniaturized Raman spectrometer. The results shows that the enhancement factor is 3.85 times higher than the control sample with single layered metal hole array. The fabrication process to obtain the HA-MIM SERS substrate is reproducible, fast, large area and low cost.     

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。     

Fabrication of uniform substrate based on silver nanoparticles decorated glycidyl methacrylate‐ethylene dimethacrylate porous material for ultrasensitive surface‐enhanced Raman scattering detection

Surface‐enhanced Raman scattering (SERS) in practical application and theoretical research mostly depends on the performance of the SERS substrate. In this study, a new SERS substrate which is based on inverted self‐assembly of Ag nanoparticles (AgNPs) on glycidyl methacrylate‐ethylene dimethacrylate (GMA‐EDMA) porous material is developed. The characterization results show the GMA‐EDMA material with intertwined pores may contribute to the distribution of the AgNPs to fabricate an ideal substrate for SERS detection. In view of the characteristics of porous material, an inverted assembly method is proposed and used in operation to avoid the adverse gravity effect which may make the AgNPs plug up the pore channel and distribute on the surface unevenly. By the inverted self‐assembly method, the AgNPs could uniformly distribute on the surface of the material stably. The prepared substrate presents ultrasensitivity and good reproducibility for SERS detection. The enhancement factor of rhodamine 6G (R6G) detection is approximately 10¹⁴ and the relative standard deviation of each characteristic peak is about 15% when the substrate is used. The substrate also shows a good performance in detecting paraquat and thymine. The ultrasensitive SERS substrate can be readily integrated into pesticide detection systems and biological sample analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

具有双共振吸收峰的Au纳米粒子制备及其拉曼表征

表面增强拉曼散射(SERS)很大程度的弥补了拉曼散射强度弱的缺点,迅速成为科研工作者们的研究热点,在食品安全、环境污染、毒品以及爆炸物检测等领域应用广泛。纳米技术的发展使得目前对于SERS的研究主要集中于金属纳米颗粒基底的制备,金属纳米粒子的种类、尺寸及形貌对SERS增强和吸收峰峰位均有影响,要获得好的增强效果,需要对金属纳米结构进行工艺优化。特别是,需要结合金属纳米粒子的结构和激励光波长,以期获得更好的增强效果。为了研究SERS增强和吸收峰之间的关系,开展了具有双共振吸收峰的金属纳米粒子的研究。首先利用FDTD Solutions仿真建模,主要针对金纳米颗粒直径、金纳米棒长径比及分布状态对共振吸收峰进行仿真,得到金纳米球理论直径在50 nm左右,金纳米棒理论长径比在3.5~4.5左右时,吸收峰分别分布在532及785 nm附近,符合多波段激励光拉曼增强条件;对于激励光偏振方向,其沿金纳米棒长轴方向偏振时吸收峰位于785 nm附近,沿金纳米球短轴方向偏振时吸收峰位于532 nm附近。然后采用种子生长法,制备了可用于多种波长激励光的双吸收峰表面增强拉曼散射基底。通过改变硝酸银用量(5,10,20,30和40 μL)、盐酸用量(0.1和0.2 mL)以及其生长时间(15,17,21和23 h)等多种工艺参数来控制金纳米棒含量,得到了同时含有金纳米球及金纳米棒的双吸收共振峰金纳米粒子。最后用该样品作为基底,罗丹明6G(R6G)作为探针分子,分别测试其在532,633和785 nm激励光入射时的SERS表征,对分析物R6G最低检测浓度均达到了10-7 mol·L-1,增强因子达到了~105,满足了多波段SERS检测的需要。     

金纳米粒子的制备及其表面增强拉曼散射效应的研究

采用多巴胺化学还原法制备了分散性良好的纳米金溶胶,并检测了其作为表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)基底的性质。粒度和透射电子显微镜测试结果表明金溶胶为平均粒径30nm左右的球形颗粒,并且紫外-可见特征吸收峰出现在520nm,为典型的金纳米颗粒特征吸收峰。以罗丹明6G(R6G)为探针分子证明了金溶胶良好的SERS增强效果,用金溶胶对除草剂敌草快(DQ)进行检测,最低检测限可达1×10-7 mol/L。结果表明所制备的金溶胶具有良好的表面增强拉曼散射活性。     

银/硅纳米孔柱阵列活性基底的SERS效应研究

以硅纳米孔柱阵列(Si-NPA)为衬底,采用浸渍法制备出一种具有规则表面形貌特征的银/硅纳米孔柱阵列(Ag/Si-NPA),并以R6G为探测目标材料,对其表面增强拉曼(SERS)效应进行了研究。结果表明,对于R6G浓度低至10-15M,Ag/Si-NPA均能表现出清晰的特征SERS峰。随着浓度的降低,R6G的荧光淬灭,所测拉曼光谱的基线降低,但特征峰峰位基本保持不变。在低浓度10-15M时得到的SERS光谱,理论上证明为单分子光谱。此外,Ag/Si-NPA活性基底具有较好的稳定性,在长达28天的自然老化过程中,Ag/Si-NPA能够保持对R6G较高的探测水平,光谱具有较好的信噪比和分辨率。Ag/Si-NPA是一种理想的SERS活性基底。     

Enhancements in intensity and thermal stability of Raman spectra based on roughened gold substrates modified by underpotential deposition of silver

In this study, electrochemically roughened gold is modified with underpotential deposition (UPD) silver to investigate the effects on enhancements in the intensity and the thermal stability of surface‐enhanced Raman scattering (SERS). The SERS of Rhodamine 6G (R6G) adsorbed on the UPD Ag‐modified Au substrate exhibits a higher intensity by six‐fold of magnitude, as compared with that of R6G adsorbedon the unmodified Au substrate. Moreover, the SERS enhancement capabilities of UPD Ag‐modified Au and unmodified Au substrates are seriously depressed at temperatures higher than 200 and 150 °C, respectively. It indicates that the modification of UPD Ag can significantly depress the thermal destruction of SERS‐active substrates. Copyright © 2009 John Wiley & Sons, Ltd.     

Improved performances on surface‐enhanced Raman scattering based on electrochemically roughened gold substrates modified with SiO2 nanoparticles

In this work, we use electrochemical oxidation–reduction cycles (ORC) methods to prepare surface‐enhanced Raman scattering (SERS)‐active gold substrates modified with SiO₂ nanoparticles to improve the corresponding SERS performances. Based on the modified substrates, the SERS of Rhodamine 6G (R6G) exhibits a higher intensity by 3‐fold of magnitude, as compared with that of R6G adsorbed on a SERS‐active Au substrate without the modification of SiO₂ nanoparticles. Moreover, the SERS enhancement capabilities of the modified and the unmodified Au substrates are seriously destroyed at temperatures higher than 250 and 200 °C, respectively. These results indicate that the modification of SiO₂ nanoparticles can improve the thermal stability of SERS‐active substrates. The aging in SERS intensity is also depressed on this modified Au substrate due to the contribution of SiO₂ nanoparticles to SERS effects. Copyright © 2009 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.     

应用球形和海胆状金混合SERS基底检测高环多环芳烃

合成了海胆状金银复合纳米材料,并与球形金纳米材料混合作为表面增强拉曼活性基底实现了对水中高环多环芳烃的痕量检测。对海胆状材料进行表征,粒径大小约为300～400 nm,表面有40～100 nm明显的刺状凸起。与球形金溶胶混合后并优化pH值及混合比例等参数,产生了优于球形金溶胶2～3倍的增强效果。利用此增强基底检测了危害严重的高环多环芳烃污染物——芘(四环)、苯并蒽(四环)、苯并芘(五环),得到的光谱数据反映出混合SERS基底有良好的重复性和稳定性,对测得光谱进行特征峰归属分析,固体拉曼光谱与水溶液SERS光谱有确定的对应关系,并且在低浓度范围多环芳烃特征峰峰强与其水溶液浓度有良好的线性关系。经计算,芘(四环)、苯并蒽(四环)、苯并芘(五环)的检测限分别为0.44,2.92和1.64 nmol·L-1。该研究的创新点为合成了海胆金纳米颗粒,与球形金溶胶混合后制成新型高效SERS检测基底;选用自制高效SERS基底,实现了高环PAHs痕量检测。结果表明,利用该方法制备的活性基底,可实现对水中高环多环芳烃的痕量检测,为检测水中高环多环芳烃提供了实验室依据。     

Synthesis of indium–silver bimetallic nanocomposites for surface-enhanced Raman scattering

We report on the synthesis of indium–silver bimetallic nanocomposites by chemical reduction method under atmospheric condition and their activity for surface-enhanced Raman scattering (SERS). It is found that the indium–silver bimetallic nanocomposites have better SERS activity with larger enhancement factors (EF) than pure silver nanoparticles with similar size. The SERS EF can reach 10⁷ for 4-mercaptobenzoic acid and 10⁹ for crystal violet and rhodamine 6G adsorbed on the nanocomposites and the detection limits can be at least down to 10^?7 and 10^?10 M, respectively. The results demonstrate that the indium–silver bimetallic nanocomposites are promising as SERS substrate for a myriad of chemical and biological sensing applications.     

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.     

Thiol‐immobilized silver nanoparticle aggregate films for surface enhanced Raman scattering

We report a novel method for the fabrication of films of silver nanoparticle aggregates that are strongly attached to Si substrates (Thiol‐immobilized silver nanoparticle aggregates or TISNA). The attachment is achieved by chemically modifying the surface of a Si(100) surface in order to provide SH groups covalently linked to the substrate and then aggregating silver nanoparticles on these thiol covered surfaces. The transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) characterization show a high coverage with single nanoparticles or small clusters and a partial coverage with fractal aggregates that provide potential hot spots for surface enhanced Raman scattering (SERS). We have confirmed the SERS activity of these films by adsorbing rhodamine 6G and recording the Raman spectra at several concentrations. By using the silver‐chloride stretching band as an internal standard, the adsorbate bands can be normalized in order to correct for the effects of focusing and aggregate size, which determine the number of SERS active sites in the focal area. This allows a quantitative use of SERS to be done. The adsorption–desorption of rhodamine 6G on TISNA films is reversible. These features make our TISNA films potential candidates for their use in chemical sensors based on the SERS effect. Copyright © 2008 John Wiley & Sons, Ltd.