Asiala Steven M, Marr James M, Gervinskas Gediminas, Juodkazis Saulius, Schultz Zachary D
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA.
Swinburne University of Technology, John St. Mail, Hawthorn, VIC 3122, Australia and Melbourne Centre for Nanofabrication, 151 Wellington Road, Clayton, VIC 3168, Australia.
Phys Chem Chem Phys. 2015 Nov 11;17(45):30461-7. doi: 10.1039/c5cp04506a.
Red-Green-Blue (RGB) dark-field imaging can direct the choice of laser excitation for Raman enhancements on nanostructured plasmonic surfaces. Here we demonstrate that black silicon (b-Si) is a structured surface that has been shown to effectively absorb broad wavelengths of light, but also enables surface enhanced Raman scattering (SERS) when coated with silver (Ag). Coating b-Si with increasing amounts of Ag results in increased dark-field scattering at discrete frequencies associated with localized plasmon resonances. The dark-field scattering was monitored by collecting a far-field image with an inexpensive complementary metal oxide semiconductor (CMOS) camera, similar to what is available on most mobile phones. Color analysis of the RGB pixel intensities correlates with the observed SERS intensity obtained with either green (532 nm) or red (633 nm) laser excitation in SERS experiments. Of particular note, the SERS response at 633 nm showed low spectral variation and a lack of background scattering compared to SERS at 532 nm. The difference in background suggests sub-radiant (dark or Fano resonances) may be associated with the SERS response at 633 nm and a non-resonant character of SERS. These results indicate that b-Si serves a template where Ag nucleates during physical vapor deposition. Increased deposition causes the deposits to coalesce, and at larger Ag thicknesses, bulk scattering is observed. Comparison with a high enhancement Ag SERS substrate further illustrates that a high density of plasmonic junctions, or hotspots, is important for maximizing the SERS response. The randomness of the b-Si substrate and the corresponding Ag nano-features contributes to a broadband spectral response and enhancement in SERS. Metal-coated b-Si is a promising SERS substrate due to its performance and facile fabrication.
红绿蓝(RGB)暗场成像可以指导在纳米结构等离子体表面上进行拉曼增强时激光激发的选择。在这里,我们证明黑硅(b-Si)是一种结构化表面,已被证明能有效吸收宽波长的光,而且在涂覆银(Ag)时还能实现表面增强拉曼散射(SERS)。用越来越多的Ag涂覆b-Si会导致在与局域等离子体共振相关的离散频率处暗场散射增加。通过使用廉价的互补金属氧化物半导体(CMOS)相机收集远场图像来监测暗场散射,这与大多数手机上可用的相机类似。RGB像素强度的颜色分析与SERS实验中用绿色(532 nm)或红色(633 nm)激光激发获得的观察到的SERS强度相关。特别值得注意的是,与532 nm处的SERS相比,633 nm处的SERS响应显示出低光谱变化且没有背景散射。背景的差异表明亚辐射(暗或法诺共振)可能与633 nm处的SERS响应以及SERS的非共振特性有关。这些结果表明,b-Si作为一种模板,在物理气相沉积过程中Ag在其上成核。沉积量增加会使沉积物聚结,并且在更大的Ag厚度下,会观察到体散射。与高增强Ag SERS基底的比较进一步表明,高密度的等离子体结或热点对于最大化SERS响应很重要。b-Si基底的随机性以及相应的Ag纳米特征有助于实现宽带光谱响应和SERS增强。金属涂覆的b-Si因其性能和易于制造而成为一种有前途的SERS基底。