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1.
表面增强拉曼散射(SERS)以其无损、超灵敏、快速检测分析等优点而备受关注,在化学和生物传感等应用领域有着极大的潜力。研制灵敏度高、重复性强、稳定性好的SERS基底,对于实现其在痕量分析、生物诊断中的实际应用具有重要意义。具有微/纳米结构的聚合物具有优异的机械性能、光学性能、耐化学性等优点。通过模板压印法,利用多孔阳极氧化铝(AAO)在聚合物聚碳酸酯(PC)表面制备一种高度有序的纳米PC尖锥阵列结构,然后通过蒸发镀膜在PC尖锥阵列上沉积一层银膜,制备了大面积Ag纳米颗粒修饰的高度有序聚合物纳米尖锥阵列。高曲率纳米针状结构顶端的银颗粒及颗粒之间狭小的纳米间隙能产生大量的SERS"热点"。这种方法得到了均匀,可重复,大面积高增强的SERS活性基底,并进一步研究了不同沉积厚度银膜的SERS特性。用扫描电子显微镜(SEM)对其进行了表征,以结晶紫作为探针分子对这种结构进行研究。结果表明:拉曼信号强度随银厚度的增加显示为先增强后减弱的趋势。基底对结晶紫的拉曼增强因子达到5.4×10~6,基底主要拉曼峰强度的RSD为10%,说明该基底具有很好的检测灵敏性和重复性。此外,基底在存放40 d后,在相同条件下仍然保持着高SERS性能,表现出很好的稳定性。整个制备过程简单易行,重复性好,制作成本非常低廉,而且能够规模化制备,可方便地作为活性基底应用于SERS研究,必将具有广阔的研究和应用前景。  相似文献   

2.
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。  相似文献   

3.
基于氧化物半导体的光催化特性,能够降解有机物分子,使表面增强拉曼散射基底得以重复使用。提出了银纳米颗粒有效修饰覆盖有石墨烯的二氧化钛纳米棒阵列(TiO_2/石墨烯/Ag)复合结构作为表面增强拉曼散射基底,并对其进行了实验研究。利用水热法制备了二氧化钛纳米棒阵列;采用湿法转移石墨烯和光照还原方法制备了TiO_2/石墨烯/Ag复合结构。用罗丹明6G(R6G)分子作为探测分子,结果表明:随着紫外光照沉积时间增加,探针分子的拉曼信号先增强后减弱;计算得到最大增强因子值约为2.6×106。此外,还对TiO_2/石墨烯/Ag复合结构的紫外自清洁特性进行了初步实验,结果表明,紫外光照射20min后,其拉曼强度下降到42.3%,具有一定的紫外清洁效果。  相似文献   

4.
表面增强拉曼散射(surface-enhanced Raman scattering,简称为SERS)能够提供有机分子的指纹特征信息,且具有灵敏度高和响应时间快等优点,是一项具有发展前景的分析技术。纳米结构SERS基底是获得SERS信号的关键。本文利用简便的电沉积方法在硅片上制备大面积的金微/纳颗粒阵列。金纳米颗粒之间存在大量狭小的纳米间隙,在光激发下产生大量的SERS"热点",从而具有很高的SERS灵敏度。而且,这种金微/纳结构具有高结构稳定性和化学稳定性。该结构对浓度低至10-12 M的罗丹明6G(R6G)具有很高的SERS灵敏性,且具有很好的SERS信号均匀性。利用这种微/纳结构阵列SERS基底,实现对水中低浓度农药甲基对硫磷的成功检测。这表明我们制备的金微/纳颗粒阵列在检测环境中的毒性有机物污染物方面具有潜在的应用前景。  相似文献   

5.
银纳米粒子修饰三维碳纳米管阵列SERS实验   总被引:1,自引:0,他引:1  
为了使表面增强拉曼散射(SERS)基底的三维聚焦体积内包含更多的“热点”,能吸附更多探针分子和金属纳米颗粒,以便获得更强的拉曼光谱信号,提出了银纳米粒子修饰垂直排列的碳纳米管阵列三维复合结构作为SERS基底,并对其进行了实验研究。利用化学气相沉积(CVD)方法制备了垂直排列的碳纳米管阵列;采用磁控溅射镀膜方法先在碳纳米管阵列上形成一层银膜,再通过设置不同的高温退火温度,使不同粒径的银纳米粒子沉积在垂直有序排列碳纳米管阵列的表面和外壁。SEM结果表明:在有序碳纳米管阵列的表面和外壁都均匀地负载了大量银纳米粒子,并且银纳米颗粒的粒径、形貌及颗粒间的间距随退火温度的不同而不同。采用罗丹明6G(R6G)分子作为探针分子,拉曼实验结果表明:R6G浓度越高,拉曼强度越强,但是R6G浓度的增加与拉曼强度增强并不呈线性变化;退火温度为450 ℃,银纳米颗粒平均粒径在100~120 nm左右,退火温度为400 ℃,银纳米颗粒平均粒径在70 nm左右,退火温度为450 ℃的拉曼信号强度优于退火温度400和350 ℃。  相似文献   

6.
本文提出一种基于气相沉积银纳米粒子和三维石墨烯-镍泡沫的复合等离激元结构.该结构是利用气相纳米团簇束流技术将高密度的银纳米粒子直接沉积于三维石墨烯-镍泡沫的表面制备而成.与传统银纳米结构相比,复合三维等离激元纳米结构具有"热点"数量多,局域场更强的特点,可作为基于表面增强拉曼技术的高灵敏度化学传感器.拉曼测试实验结果表明,该三维纳米结构在表面增强拉曼检测中可获得灵敏度高,重复性好的探针拉曼信号.通过进一步的理论模拟,发现该三维等离激元结构中增强的拉曼信号主要归因于纳米粒子与纳米粒子之间以及纳米粒子与石墨烯-镍泡沫衬底之间的多重近场耦合效应.  相似文献   

7.
表面增强拉曼散射(SERS)是一种广泛应用于化学反应检测、医学诊断和食品分析等领域的高灵敏度光谱技术.基底结构的构建对提高探针分子的SERS信号有非常重要的影响.本文利用聚甲基丙烯酸甲酯(PMMA)包裹银纳米颗粒制备了一种三维金字塔立体复合SERS基底,实现了对罗丹明6G (R6G)分子的高灵敏度检测.通过调节银纳米颗粒在PMMA丙酮溶液中的分散密度,实现了光在金字塔谷内的有效振荡,既保证了三维结构高密度的"热点"效应,又避免了由于金属-分子相互作用引起的吸附探针分子变形导致的信号失真等问题.同时,有效防止了银纳米颗粒的氧化,为探针分子提供更大的电磁增强作用范围,使增强的拉曼信号产生稳定的输出.此研究结果不仅提供了一种高性能、可重复使用的SERS基底的有效策略,也会对未来设计改进三维结构的SERS基底有指导意义.  相似文献   

8.
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。  相似文献   

9.
本文提出一种基于气相沉积银纳米粒子和三维石墨烯-镍泡沫的复合等离激元结构.该结构是利用气相纳米团簇束流技术将高密度的银纳米粒子直接沉积于三维石墨烯-镍泡沫的表面制备而成.与传统银纳米结构相比,复合三维等离激元纳米结构具有"热点"数量多,局域场更强的特点,可作为基于表面增强拉曼技术的高灵敏度化学传感器.拉曼测试实验结果表明,该三维纳米结构在表面增强拉曼检测中可获得灵敏度高,重复性好的探针拉曼信号.通过进一步的理论模拟,发现该三维等离激元结构中增强的拉曼信号主要归因于纳米粒子与纳米粒子之间以及纳米粒子与石墨烯-镍泡沫衬底之间的多重近场耦合效应.  相似文献   

10.
本文将合成的直径为10 nm的正电荷金纳米颗粒通过静电作用高密度自组装到带负电荷的长链λ-DNA分子上, 形成了高密度的具有纳米间隙的金纳米颗粒网络结构。研究了孤立的金纳米颗粒和所自组装的金纳米颗粒-DNA复合材料作为表面增强拉曼散射(SERS)基底的活性。原本对SERS信号响应较弱的10 nm直径的金纳米颗粒, 在自组装到DNA上形成具有纳米间隙的金纳米颗粒网络后, 产生了均匀、一致、强烈的SERS增强响应。我们利用用该基底对罗丹明G(R6G)、吡啶(Py)和对巯基苯胺(4-ATP)等不同类型的小分子化合物进行SERS检测的结果表明, 此方法制备SERS基底产率高、均一, 具有较好的SERS增强效果好, SERS信号稳定性和重复性相对常规孤立的金纳米颗粒SERS基底有很大提高。  相似文献   

11.
Highly ordered arrays of thiolated β‐cyclodextrin (HS‐β‐CD) functionalized Ag‐nanorods (Ag‐NRs) with plasmonic antennae enhancement of electrical field have been achieved for encapsulation and rapid detection of polychlorinated biphenyls (PCBs). The large‐area ordered arrays of rigid Ag‐NRs supported on copper base were fabricated via porous anodic aluminum oxide (AAO) template‐assisted electrochemical deposition. The inter‐nanorod gaps between the neighboring Ag‐NRs were tuned to sub‐10 nm by thinning the pore‐wall thickness of the AAO template using diluted H3PO4. The nearly perfect large‐area ordered arrays of Ag‐NRs supported on copper base render these systems excellent in surface‐enhanced Raman scattering (SERS) performance with uniform electric field enhancement, as testified by the SERS spectra and Raman mappings of rhodamine 6 G. Furthermore, the Ag‐NRs were functionalized with HS‐β‐CD molecules so as to capture the apolar PCB molecules in the hydrophobic cavity of the CD. Compared to the ordinary undecorated SERS substrates, the HS‐β‐CD modified Ag‐NR arrays exhibit better capture ability and higher sensitivity in rapid detection of PCBs. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

12.
Two types of highly Raman-enhancing arrays substrates were fabricated using anodic aluminum oxide (AAO) templates by controlling the AAO template temperature and evaporated silver thickness during e-beam evaporating: complex patterned Ag nanoparticle arrays abundant in sub-5 nm gaps (type I); hexagonal Ag nanopore arrays (type II). The surface enhanced Raman scattering (SERS) enhancement factors (EF) of both substrates are estimated experimentally to exceed 105, especially that of type I reaches 107 due to the existence of numerous sub-5 nm gaps. The simulation using finite-difference time-domain (FDTD) method confirmed that gap effect has significantly improved the substrates’ SERS activity.  相似文献   

13.
The surface‐enhanced Raman scattering substrate of Ag–Ag nanocap arrays are prepared by depositing Ag film onto two‐dimensional (2D) polystyrene colloidal nanosphere templates. When the original colloidal arrays are used as the substrate for Ag deposition, surface‐enhanced Raman scattering (SERS) enhancements show the strong size‐dependence behaviours. When O2‐plasma etched 2D polystyrene templates are used as the substrate for Ag deposition to form nanogaps, the gap sizes between adjacent Ag nanocaps from 5 to 20 nm generate even greater SERS enhancements. When SiO2 coverage is deposited to isolate the Ag nanocaps from the neighbours, the SERS signals are enhanced more. The significant SERS effects are due to the coupling between Ag nanocaps controlled by the distance, which enhances the local electric‐field intensity. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

14.
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.  相似文献   

15.
Substrates with complex and hierarchical nanostructure are widely investigated in surface‐enhanced Raman scattering (SERS), but it remains challenging to improve the structural uniformity and stability. Herein, a novel method is proposed: confined spheroidization. Unique configurations of hierarchical metallic nanoparticle arrays (HMNA) are successfully fabricated by confined spheroidizing on anodic aluminum oxide templates. By utilizing the confined effect of the holes, a series of large particles inside the hole and small particles arranged on the hole wall are obtained after thermal annealing. The size and distribution of nanoparticles strongly depend on the hole size, the thickness of the hole wall, and the deposition thickness of metal layer. COMSOL simulations demonstrate good SERS activity of the HMNA, with a low detection limit of ≈10?8 m for crystal violet (CV) and the enhancement factor of ≈ 4.97 × 107 at the 1160 cm?1 mode of CV. The relative standard deviation of 6.23% from 59 random spots and a 9.24% signal variation among ten substrates are achieved, showing good SERS signal reproducibility of the HMNA. This simple and low‐cost technique makes it possible to prepare 3D hierarchical ordered micro–nanostructures by one‐step, showing prospect applications in SERS‐based detection and plasmonic materials.  相似文献   

16.
Semiordered Ag nanorod arrays are fabricated by template oblique angle deposition (OAD) using regular Au nano‐post arrays with different diameters as seed patterns. The Au nano‐post arrays do not give an observable surface‐enhanced Raman scattering (SERS) activity under our detection configuration, whereas the patterned Ag nanorod arrays can produce a very strong SERS signal. These SERS intensities increase monotonically with the decrease in the diameter and separation of the Ag nanorods, which demonstrates that one can improve the SERS detection by tuning the diameter and separation of the Ag nanorods, and the template OAD method can help produce more uniform, reproducible, and sensitive Ag nanorod SERS substrates. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

17.
Carbendazim (MBC) is a fungicide widely used in agriculture, and there are serious concerns regarding the health risks that could be caused by this fungicide. Here, we explore its ultrasensitive detection by surface‐enhanced Raman scattering (SERS). First, to obtain maximum SERS signal, the adsorption of the target molecule onto metallic surface is essential. Therefore, we study the adsorption of the MBC onto the nanoparticle surface by SERS under different experimental conditions, such as different synthesis methods of nanoparticle, variable excitation wavelength, and fungicide concentration with the aim to detect MBC at low concentrations. Experiments are carried out with three kinds of colloidal nanoparticles: Ag and Au reduced by citrate and Ag reduced by hydroxylamine. However, mainly Ag colloids are highly efficient in the SERS detection of MBC. In addition, theoretical calculations of MBC Raman spectrum and that of the surface complex are used to help with the understanding the mechanisms responsible for the interaction between MBC and Ag. Ultraviolet–visible absorption spectroscopy showed displacement to the red of the plasmon resonance of Ag colloid in the presence of MBC. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

18.
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.  相似文献   

19.
The fabrication of flexible surface-enhanced Raman scattering (SERS) substrates for sensitive detection on uneven or irregular surfaces is challenging. In this study, a flexible dual plasmonic SERS (FDPS) substrate rationally constructed using Au nanoparticle (AuNP) arrays/aligned Ag nanowires (AgNWs) and elastic polyurethane (PU) is demonstrated. It exhibits high sensitivity (detection limit of 10−8 m for melamine and 10−10 m for malachite green) and excellent reproducibility. The well-designed structure of AuNP arrays/aligned AgNWs fabricated using block copolymer self-assembly and oil–water–air interfacial self-assembly successfully enhances the electromagnetic field through plasmonic coupling. In addition, the FDPS substrate retains a high SERS sensitivity after exposure to air at room temperature for 30 days because of the high stability of AuNP arrays and antioxidation characteristic of the PU covered on the aligned AgNWs. Even after undergoing stretching, bending, and twisting for 100 cycles, the FDPS substrate maintains a stable SERS activity owing to the introduction of the elastic PU. This study demonstrates a potential application of SERS detection under practical conditions for irregular surfaces and may be helpful in the development of flexible sensors.  相似文献   

20.
It is demonstrated that the surface-enhanced Raman scattering (SERS) intensity of R6G molecules adsorbed on a Ag nanoparticle array can be controlled by tuning the size and height of the nanoparticles. A firm Ag nanoparticle array was fabricated on glass substrate by using nanosphere lithography (NSL) combined with reactive ion etching (RIE). Different sizes of Ag nanoparticles were fabricated with seed polystyrene nanospheres ranging from 430 nm to 820 nm in diameter. By depositing different thicknesses of Ag film and lifting off nanospheres from the surface of the substrate, the height of the Ag nanoparticles can be tuned. It is observed that the SERS enhancement factor will increase when the size of the Ag nanoparticles decreases and the deposition thickness of the Ag film increases. An enhancement factor as high as 2×106 can be achieved when the size of the polystyrene nanospheres is 430 nm in diameter and the height of the Ag nanoparticles is 96 nm. By using a confocal Raman mapping technique, we also demonstrate that the intensity of Raman scattering is enhanced due to the local surface plasmon resonance (LSPR) occurring in the Ag nanoparticle array.  相似文献   

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