Experimental demonstration of surface selection rules for SERS on flat metallic surfaces

Ru, Eric C. Le; Meyer, Stefan; Artur, Camille; Etchegoin, P.; Grand, Johan; Lang, Philippe; Maurel, François

doi:10.1039/c1cc10484e

Cited by 123 publications

(102 citation statements)

References 13 publications

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“…The author's work in 1982 gave theoretical grounds for local field polarization. Recently, Ru et al have experimentally validated Moskovits theory by studying polarization and incident angle dependences of the SERS signals [51]. Similar studies using TERS can offer more insights into the Raman SSR as the Raman signal can be directly related to the molecules present under the tip.…”

Section: Understanding Tersmentioning

confidence: 95%

Nanoscale Insights into Enhanced Raman Spectroscopy

Rzeznicka¹,

Horino²

2018

Raman Spectroscopy

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Enhanced Raman spectroscopies, such as surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS), are based on the amplification of intrinsically weak Raman signals of a molecule by metallic nanostructures. The main enhancement is attributed to electromagnetic enhancement. Chemical effects, such as formation of a surface complex, or a charge-transfer complex, co-adsorbed anion effect, also add to the enhancement of the signal. Using SERS, it has been difficult to study details of chemical enhancement and polarization effects due to limited optical resolution of the technique and usage of roughened metal surfaces. These obstacles were overcome with the development of the TERS technique. TERS has extended Raman spectroscopy into the nanoscale region. In this chapter, nanoscale insights into surface chemistry that lead to Raman signal enhancement are described. The effect of molecular binding and orientation as well as commonly used in SERS chloride activation of metal surfaces is discussed. Finally, we describe the future prospects of TERS and the challenges that keep us from harnessing the full potential of the technique.

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Section: Understanding Tersmentioning

confidence: 95%

Nanoscale Insights into Enhanced Raman Spectroscopy

Rzeznicka¹,

Horino²

2018

Raman Spectroscopy

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“…SERS can also be used to study pH‐dependent behaviors . SERS has high sensitivity, but its intensity may be significantly changed depending on the surface distances . For this reason, simple desorption reactions are conducted using labeled Raman dyes such as para ‐aminothiophenol and Nile Blue because of the rather drastic change of the local enhancements from the surfaces …”

Section: Introductionmentioning

confidence: 99%

Surface anchoring mode‐dependent hydrolysis reactions of hydrazone groups on gold examined by pH‐dependent Raman spectroscopy

Joo

2015

J Raman Spectroscopy

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We conducted a comparative study of the pH‐dependent anchoring behaviors of 3‐methyl‐2‐benzothiazolinone hydrazone (3M2BH) and benzophenone hydrazone (BPH) on gold nanoparticles (AuNPs) by means of interfacial Raman spectroscopy. We found that several bands of 3M2BH in the highly alkaline pH region disappeared as the colloidal conditions became more neutral and acidic. The vibrational band at 919, 1174, and 1222 cm−1 at pH 10.0 disappeared below pH 9.2, which may be because of the hydrolysis reactions that cleave the labile N―NH2 group of 3M2BH, indicating a rather perpendicular orientation via the sulfur atom at the surfaces. A fairly high transition pH value was assumed to be because of the interaction of the N―NH2 group in the vicinity of the surfaces. Several characteristic bands, including 1584 and 1617 cm−1, also exhibited different intensities, suggesting that the adsorbates on Au surfaces underwent structural transformations of the N―NH2 group after the pH value became neutral or acidic. These changes were not observed for BPH, presumably because of the direct and robust binding of the hydrazone onto Au surfaces. Our results revealed that the pH‐dependent cleavage reactions may vary depending on the surface anchoring modes of the adsorbates. Copyright © 2015 John Wiley & Sons, Ltd.

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“…The variation in enhancement of molecular signals of the same peak could be accounted for the different local field polarizations of the molecule on the surface. 22 The effect of the sandwich structure on gold shows extraordinary enhancements compared to that on mica. The observed EF is as large as 68 for the molecular peak at 1530 cm À1 , which corresponds to the estimated enhancement range for chemical enhancement.…”

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confidence: 97%

“…This relatively small enhancement factor indicates that the underlying mechanism is dominated by chemical enhancement on a flat gold surface. 22 The Raman spectrum of CuPc sandwiched between single layer graphene and gold is plotted red in Fig. 1(b).…”

mentioning

confidence: 99%

“…20,21 Similarly, flat gold is known to be a fluorescence quencher and it shows SERS efficiency. 22 Therefore, the sandwich structure -CuPc between graphene and atomically flat gold -provides a well-defined platform for the investigation of opto-electronics on the nanoscale, including photon-induced electron transfer. In particular, it allows to address the question, whether the mainly CM-dominated GERSeffect can be enhanced further through a flat SERS substrate.…”

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confidence: 99%

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