Mid-infrared-perturbed molecular vibrational signatures in plasmonic nanocavities.
Mid-infrared-perturbed molecular vibrational signatures in plasmonic nanocavities.
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DOI：
10.1038/s41377-022-00709-8
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发表时间：
2022-01-19
期刊：
影响因子：
--
通讯作者：
Baumberg JJ
中科院分区：
文献类型：
--
作者：
Chikkaraddy R;Xomalis A;Jakob LA;Baumberg JJ
表面增强拉曼散射（Sers）技术的最新发展使人们能够在室温下观察到真实的单键振动。相比之下，中红外（MIR）振动光谱仅限于低效的慢速检测。在这里，我们开发了一种新的方法用于MIR传感使用Sers。该方法利用箔上纳米颗粒（NPoF）纳米腔，其在由单层分子形成的相同纳米间隙中支持可见光和MIR等离子体热点。来自单个NPoF纳米腔的分子Sers信号在MIR光子的存在下被调制。这种调制的强度取决于MIR波长，并且在放置在箔下的SiO2或聚苯乙烯的6-12 μm吸收带处最大化。使用单光子锁定检测方案，我们在几个100 ns的信号的上升和衰减的时间解决。我们的观察结果表明，SiO2的声子共振可以在Reststrahlen带内捕获强烈的MIR表面等离子体激元，通过可逆地扰动困在纳米结构裂缝中的局部几nm厚的水壳来调谐可见光波长局部等离子体激元。这为光学力学耦合纳米级键振动提供了新的方法，有可能将检测极限降低到单光子和单分子范围。在等离子体纳米腔基底的声子带中吸收的中红外光在亚μs时间尺度上扰动拉曼散射信号，从而允许开发单光子中红外探测器。
Recent developments in surface-enhanced Raman scattering (SERS) enable observation of single-bond vibrations in real time at room temperature. By contrast, mid-infrared (MIR) vibrational spectroscopy is limited to inefficient slow detection. Here we develop a new method for MIR sensing using SERS. This method utilizes nanoparticle-on-foil (NPoF) nanocavities supporting both visible and MIR plasmonic hotspots in the same nanogap formed by a monolayer of molecules. Molecular SERS signals from individual NPoF nanocavities are modulated in the presence of MIR photons. The strength of this modulation depends on the MIR wavelength, and is maximized at the 6–12 μm absorption bands of SiO2 or polystyrene placed under the foil. Using a single-photon lock-in detection scheme we time-resolve the rise and decay of the signal in a few 100 ns. Our observations reveal that the phonon resonances of SiO2 can trap intense MIR surface plasmons within the Reststrahlen band, tuning the visible-wavelength localized plasmons by reversibly perturbing the localized few-nm-thick water shell trapped in the nanostructure crevices. This suggests new ways to couple nanoscale bond vibrations for optomechanics, with potential to push detection limits down to single-photon and single-molecule regimes. Mid-infrared light absorbed in the phonon-bands of a plasmonic nanocavity substrate perturb the Raman scattering signals on sub-µs timescales, allowing development of single-photon mid-infrared detectors.
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DOI：
10.1021/acs.jpclett.6b00986
发表时间：
2016-06-16
期刊：
The journal of physical chemistry letters
影响因子：
--
作者：
Benz F;Chikkaraddy R;Salmon A;Ohadi H;de Nijs B;Mertens J;Carnegie C;Bowman RW;Baumberg JJ
通讯作者：
Baumberg JJ
影响因子：
38.3
作者：
Efetov, Dmitri K.;Shiue, Ren-Jye;Englund, Dirk
通讯作者：
Englund, Dirk
影响因子：
35
作者：
Dam, Jeppe Seidelin;Tidemand-Lichtenberg, Peter;Pedersen, Christian
通讯作者：
Pedersen, Christian
影响因子：
7
作者：
Chikkaraddy R;Baumberg JJ
通讯作者：
Baumberg JJ
影响因子：
4.4
作者：
Asay, DB;Kim, SH
通讯作者：
Kim, SH