Electronic Thesis and Dissertation Repository

Degree

Doctor of Philosophy

Program

Chemistry

Supervisor

Francois Lagugné-Labarthet

Abstract

A deep understanding of the chemical composition of surfaces, interfaces or nanoscale structure with a high spatial resolution is an important goal in nanoscience and nanotechnology. Structural information can be collected using a variety of high spatial resolution techniques such as atomic force microscopy (AFM), scanning tunneling microscopy (STM), scanning electron microscopy (SEM), or transmission electron microscopy (TEM). Nevertheless, these methods do not offer molecular information such as vibrational spectroscopy techniques that allow one to collect molecular or lattice vibrations yielding to a precise picture of the molecular interactions in bulk materials as well as in surfaces and interfaces. Unfortunately optical spectroscopy techniques are limited in terms of spatial resolution and sensitivity due to the poor signal/noise ratio of the localized measurement.

Surface- and tip-enhanced Raman spectroscopy (SERS and TERS) are advanced spectroscopic techniques, which are becoming widely used and show a great potential for the structural characterisation of biological systems. Surface-enhanced spectroscopy (SERS) was developed to improve the sensitivity of the chemical measurements by using rough silver or gold surfaces. The challenge of the simultaneous improvement of the spatial resolution and sensitivity was addressed by combining high resolution optical microscopy with the high sensitivity of surface-enhanced spectroscopy and was termed tip-enhanced Raman spectroscopy (TERS).

In this thesis, gap-mode TERS is developed for the study of a variety of materials. TERS is used in conjunction with gold nanoplates to serve as an ultraflat substrate that can possibly be functionalized. TERS investigation of monolayers adsorbed onto gold nanoplates such as alkoxy substituted azobenzene thiol and 4-nitrothiophenol is conducted. The monolayer is probed with a silver coated AFM tip in order to obtain the largest electromagnetic field enhancement and the effect of the excitation (linearly or radially polarized) is conducted. TERS is also used to probe graphene flakes and differentiate the edges of a few-layer graphene flakes with a spatial resolution better than 20 nm. Last, TERS was used to investigate single DNA molecules deposited onto gold nanoplates. The DNA, cDNA and pure plasmid were investigated with TERS probing the distribution of nucleobases at a specific location with a spatial resolution which was, in the best conditions below 10 nm.


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