Electronic and vibrational surface-enhanced Raman scattering: from atomically defined Au(111) and (100) to roughened Au.
Electronic and vibrational surface-enhanced Raman scattering: from atomically defined Au(111) and (100) to roughened Au.
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DOI：
10.1039/d0sc02976a
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发表时间：
2020-08-03
期刊：
影响因子：
8.4
通讯作者：
Ikeda K
中科院分区：
文献类型：
--
作者：
Inagaki M;Isogai T;Motobayashi K;Lin KQ;Ren B;Ikeda K
在表面增强拉曼光谱中，振动峰叠加在背景连续谱上，这被称为一个主要的实验异常。这在评估振动信息时是有问题的，特别是在低于200 cm-1的低拉曼位移区域，其中背景信号占主导地位。在此，我们提出了一个严格的比较正常的拉曼和表面增强拉曼光谱的原子定义的表面的Au（111）或Au（100）有和没有分子吸附。它清楚地表明，背景连续的起源很好地解释了在Au的导带的电子拉曼散射的局部场增强。在低拉曼位移区域，电子拉曼散射获得额外的强度，可能是由于通过表面粗糙度的动量转移的动量守恒规则的松弛。基于光谱背景产生的机理，我们还提出了一种实用的方法，通过在斯托克斯和反斯托克斯分支的宽范围内降低热因子、散射效率因子和珀塞尔因子，从测量的原始光谱中提取金属/电介质界面处的电子和振动信息。这种方法不仅使我们能够分析隐藏在低拉曼位移区域的振动特征，而且还可以从表面增强拉曼光谱中估计更可靠的局部温度。从表面增强拉曼光谱中明确地提取了金属/电介质界面处的电子和振动信息。
In surface-enhanced Raman spectra, vibrational peaks are superimposed on a background continuum, which is known as one major experimental anomaly. This is problematic in assessing vibrational information especially in the low Raman-shift region below 200 cm−1, where the background signals dominate. Herein, we present a rigorous comparison of normal Raman and surface-enhanced Raman spectra for atomically defined surfaces of Au(111) or Au(100) with and without molecular adsorbates. It is clearly shown that the origin of the background continuum is well explained by a local field enhancement of electronic Raman scattering in the conduction band of Au. In the low Raman-shift region, electronic Raman scattering gains additional intensity, probably due to a relaxation in the conservation of momentum rule through momentum transfer from surface roughness. Based on the mechanism for generation of the spectral background, we also present a practical method to extract electronic and vibrational information at the metal/dielectric interface from the measured raw spectra by reducing the thermal factor, the scattering efficiency factor and the Purcell factor over wide ranges in both the Stokes and the anti-Stokes branches. This method enables us not only to analyse concealed vibrational features in the low Raman-shift region but also to estimate more reliable local temperatures from surface-enhanced Raman spectra. Both electronic and vibrational information at the metal/dielectric interface were explicitly extracted from surface-enhanced Raman spectra.
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证明 Au 的光致发光是等离子体金属的电子非弹性光散射：SERS 背景的起源。
影响因子：
10.8
作者：
Hugall JT;Baumberg JJ
通讯作者：
Baumberg JJ
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：
3.7
作者：
Huemmer, T.;Garcia-Vidal, F. J.;Zueco, D.
通讯作者：
Zueco, D.
影响因子：
3.7
作者：
Butcher, Dennis P., Jr.;Boulos, Stefano P.;Gewirth, Andrew A.
通讯作者：
Gewirth, Andrew A.
影响因子：
10.8
作者：
Cai, Yi-Yu;Sung, Eric;Link, Stephan
通讯作者：
Link, Stephan