ACS Appl Mater Interfaces. 2019 Jan 16;11(2):2273-2281. doi: 10.1021/acsami.8b17876. Epub 2019 Jan 3.
We report the first observation of symmetry breaking-induced mode splitting in coupled gold-silver alloy nanodisk array (ANA). According to the plasmonic hybridization picture, the original localized surface plasmon resonance (LSPR) of individual nanodisk is split into a pair of high and low energy modes when placed in between a superstrate and a substrate. Although well studied in single silver nanoparticles, the high energy mode has been largely suppressed in gold nanoparticles, which nevertheless are more chemically robust and have superior environmental stability. Herein, we show that the high energy mode can be partially restored and precisely engineered to ∼540 nm for silver-rich alloy nanodisk which has excellent environmental stability. However, peak broadening and red-shifting occur due to plasmonic dephasing when the nanodisk diameter increases. We next demonstrate that a far-field coupled ANA fabricated by low-cost nanosphere lithography can fully restore the high energy mode with electric field concentration extended into the superstrate, thereby imparting greater sensitivity to local refractive index changes. The high energy mode at 540 nm is of key importance for color change detection using low-cost RGB cameras/human vision and broadband light sources (e.g., the sun). The index sensitivity of ANA is the highest among existing plasmonic arrays (particles or holes) within a similar resonance wavelength region. We demonstrate colorimetric detection of sub-nanomolar and sub-monolayer biotin-streptavidin surface binding with a smartphone camera and a white light lamp. The high performance yet low-cost fabrication and detection technology could potentially result in affordable point-of-care biosensing technologies.
我们首次观察到在金-银合金纳米盘阵列(ANA)中对称破缺诱导的模式分裂。根据等离子体杂化图像,当放置在上层和下层之间时,单个纳米盘的原始局域表面等离子体共振(LSPR)会分裂成一对高能和低能模式。虽然在单个银纳米粒子中得到了很好的研究,但在金纳米粒子中,高能模式却受到了很大的抑制,尽管金纳米粒子在化学上更稳定,具有更好的环境稳定性。在此,我们表明,对于具有优异环境稳定性的富银合金纳米盘,高能模式可以部分恢复并精确设计为∼540nm。然而,当纳米盘直径增加时,由于等离子体退相,会出现峰展宽和红移。我们接下来证明,通过低成本的纳米球光刻技术制造的远场耦合 ANA 可以完全恢复高能模式,从而将电场集中扩展到上层,从而赋予更大的局部折射率变化灵敏度。在 540nm 处的高能模式对于使用低成本 RGB 相机/人眼和宽带光源(例如太阳)进行颜色变化检测至关重要。ANA 的折射率灵敏度在类似共振波长区域内的现有等离子体阵列(粒子或孔)中是最高的。我们使用智能手机相机和白光灯泡演示了亚纳摩尔和亚单层生物素-链霉亲和素表面结合的比色检测。这种高性能且低成本的制造和检测技术有可能实现负担得起的即时护理生物传感技术。
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