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Quantification of the Enhancement Factor in Surface-Enhanced Raman Scattering

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posted on 10.11.2021, 03:12 by Blackie, Evan

This thesis presents a rigorous stepwise methodology towards the accurate measurement and quantification of the SERS enhancement factor (EF), the key parameter in describing the SERS effect. The work represents, we believe, a successful attempt to resolve some of the inconsistencies in the literature and to refocus the field by emphasizing the importance of consistent definitions and rigorous quantification to elucidate matters of fundamental importance in SERS. The success in our approach is that it combines careful experimental measurements upon a sound theoretical framework, and utilizes a 'toolbox' of techniques developed in recent years, such as bi-analyte SERS (BiASERS) techniques for single-molecule (SM) detection, and isotopic editing. In experimental work, we measure the bare Raman cross-sections of five common probes used in SERS as a first step in measuring the analytical enhancement factor (AEF) and single-molecule enhancement factor (SMEF). The methodology in measuring these EFs involved the use of a reference standard of known cross-section along with a careful characterization of the scattering volume through beam profiling experiments. As a guide to validating the reference cross-section we make extensive use of density functional theory (DFT) calculations to obtain estimates for the intrinsic Raman cross-sections of small, non-resonant probes. The results of this work showed that previous upper limits for the EF reported in the literature of 1014 were based on a faulty normalization of the EF. In fact, EFs of 108 were sufficient to see single molecules, which is much lower than previously expected; under optimum conditions, even lower EFs, possibly down to 105 could be sufficient for the SM detection of resonant probes. As a valuable extension of BiASERS, we elaborate on the synthesis of isotopic analogues of a rhodamine dye as ideal partners for SM experiments. The synthesis and definitive characterization of these probes enable their use in an experiment to determine the SM regime in a liquid colloidal sample. Isotopically edited dyes such as these, in combination with the methodologies of EF quantification outlined herein, set the standard for those interested in accurate quantification of the SERS effect. This approach is useful in terms of both basic theoretical questions and applications such as the effective comparison of SERS substrates. Finally, we extend the techniques developed over the thesis to a long-standing and largely unresolved question in SERS: What is the minimum intrinsic Raman cross-section that can be measured as a single molecule in standard SERS conditions. In this work, we explore the SM detection non-resonant probes, which are the molecules of interest for many practical applications such as forensics and biological assays. Specifically, we demonstrate the successful SM detection of isotopically edited adenine probes.


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Date of Award



Te Herenga Waka—Victoria University of Wellington

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Degree Grantor

Te Herenga Waka—Victoria University of Wellington

Degree Level


Degree Name

Doctor of Philosophy

Victoria University of Wellington Item Type

Awarded Doctoral Thesis



Victoria University of Wellington School

School of Chemical and Physical Sciences


Etchegoin, Pablo