波纹状银纳米线的制备及其SERS性能研究

Fabrication of Silver Nanowires with Corrugated-Surface and Its SERS Performance

首先通过传统的多元醇方法合成了表面光滑的银纳米线,然后利用Fe(NO3)3作为刻蚀剂在室温条件下对合成的银纳米线进行刻蚀得到了具有波纹状表面的银纳米线.通过扫描电镜(SEM)分析表明:银纳米线的表面粗糙程度随着刻蚀剂量的增加而增加,但过量的刻蚀剂又会导致纳米线的断裂甚至形成球状颗粒;当刻蚀剂的量为100μL时,获得了波纹状表面的银纳米线.对结晶紫(CV)的表面增强拉曼光谱(SERS)结果表明,这种波纹状银纳米线的拉曼信号强度比表面光滑的银纳米线提高了约5倍,其检测限可低至10-10 mol/L.此外,这种优势还可以延伸到敏感性检测10-9mol/L的对巯基吡啶(4-Mpy)分子,可以作为一种普适、有效的SERS活性基底.

In order to create the effective number of surface-enhanced Raman scattering(SERS) active 'hot spots' on the one-dimensional nanostructure surfaces for ensuring the maximum enhancement of SERS signal, smooth silver nanowires(Ag NWs) were firstly synthesized by the conventional polyol method, and then the smooth silver nanowires were subjected to chemical etching by the Fe(NO3)3 aqueous solution at room temperature to obtain corrugated silver nanowires. This corrugated silver nanowires were systematically characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD) microscopy, Ultraviolet-visible(UV-vis) extinction spectroscopy and surface enhanced Raman spectroscopy(SERS). The SEM image of smooth silver nanowires shows that had a diameter of ca. 120 nm and lengths of about tens of micrometers, while the average thickness of corrugated nanowires was only about 100 nm. The XRD patterns for both smooth and corrugated silver nanowires indicate that the fcc structure was preserved after chemical etching. From the measurement of UV-vis spectra we can see that after the smooth silver nanowires were subjected to chemical etching, only one broad surface plasmon peak was observed at ca. 386 nm while two significant peaks were observed at 353 and 392 nm for the smooth silver nanowires. The slight blue-shift of this peak from 392 to 386 nm could be contributed by the decrease in diameter of silver nanowires, whereas the broadening of the plasmon peak was probably a result of increased surface roughness. The SEM images showed that the surface roughness of silver nanowires was dependent on the amount of Fe(NO3)3, by increasing the amount of Fe(NO3)3 added into the silver nanowires solution, the surface of silver nanowires become more and more rough. However, as the excess amount of etchant added, most silver nanowires would broke off into shorter rods, and even spherical particles. Raman analyses of crystal violet(CV) indicated that the SERS intensity changes depending on the surface roughness of etched silver nanowires, and the silver nanowires with corrugated surfaces exhibited higher enhancement of SERS signal than the smooth silver nanowires. In addition, the SERS detection of CV and 4-mercaptopyridine(4-Mpy) molecules exhibited high detection sensitivity and the detection concentration were as low as 10-10 and 10-9 mol/L, respectively, which means that the corrugated silver nanowires could be an efficient SERS active substrate.