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The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene. / Robert Rickman

Swansea University Author: Robert Rickman

Abstract

Tip-enhanced Raman spectroscopy (TERS) is a scanning probe technique that utiHscs a confined, ovanescent field at the tip apex to conduct optical characterisation of a surface at length-scales below the diffraction limit. This thesis details the development of a new TER.S system based upon a shear-f...

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Published: 2013
Institution: Swansea University
Degree level: Doctoral
Degree name: Ph.D
URI: https://cronfa.swan.ac.uk/Record/cronfa42581
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first_indexed 2018-08-02T18:55:03Z
last_indexed 2018-08-03T10:10:32Z
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spelling 2018-08-02T16:24:29.7433976 v2 42581 2018-08-02 The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene. 600e868e399df735d471a6b8bf967b9a NULL Robert Rickman Robert Rickman true true 2018-08-02 Tip-enhanced Raman spectroscopy (TERS) is a scanning probe technique that utiHscs a confined, ovanescent field at the tip apex to conduct optical characterisation of a surface at length-scales below the diffraction limit. This thesis details the development of a new TER.S system based upon a shear-force scanning probe microscope (SPM) which sits atop an inverted microscope configured for bottom illumination geometry and coupled to a Raman spectrometer. The system has been optimised for use with solid silver probes and 532 nm illumination. Measurement procedures, automated scripts and data analysis software have been developed that allow reliable alignment of the tip; complex automated mapped measurements; and post processing which produces visual summary sheets to facilitate rapid review of a TERS experiment. Enhanced TERS spectra have been demonstrated on ultra-thin Rhodamine 6G films, self assembled monolayers (SAM) of thiophenole molecules, ultra-thin graphitic films and on multilayered graphene. Improvements in fabrication and alignment procedures have reduced the setup time between fabrication and approach to 20 minutes and improved the reliability of TERS tips with ~ 50% of tips demonstrating TERS activity. Using TERS, heightened defect sensitivity was observed on graphene edges, folds and overlapping regions. The TERS contrast of the defect induced D band was ~ 7.5 times the contrast of the graphene G band. Calculations show that the phonons correlating to the D and G bands interact differently with the enhanced TERS field and that the for certain defect types the D band experiences greater enhancement. Defects play an important role in tailoring the electronic and chemical properties of graphene which is key to the development of graphene based devices. The localised structural and spectral information makes TERS a highly promising tool for the characterisation of defects in graphene. This work demonstrates the potential of TERS for this exciting and important application. E-Thesis Electrical engineering. 31 12 2013 2013-12-31 COLLEGE NANME Physics COLLEGE CODE Swansea University Doctoral Ph.D 2018-08-02T16:24:29.7433976 2018-08-02T16:24:29.7433976 Faculty of Science and Engineering School of Biosciences, Geography and Physics - Physics Robert Rickman NULL 1 0042581-02082018162505.pdf 10805339.pdf 2018-08-02T16:25:05.7500000 Output 20769419 application/pdf E-Thesis true 2018-08-02T16:25:05.7500000 false
title The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene.
spellingShingle The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene.
Robert Rickman
title_short The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene.
title_full The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene.
title_fullStr The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene.
title_full_unstemmed The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene.
title_sort The development of tip-enhanced Raman spectroscopy for defect characterisation in graphene.
author_id_str_mv 600e868e399df735d471a6b8bf967b9a
author_id_fullname_str_mv 600e868e399df735d471a6b8bf967b9a_***_Robert Rickman
author Robert Rickman
author2 Robert Rickman
format E-Thesis
publishDate 2013
institution Swansea University
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Biosciences, Geography and Physics - Physics{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Biosciences, Geography and Physics - Physics
document_store_str 1
active_str 0
description Tip-enhanced Raman spectroscopy (TERS) is a scanning probe technique that utiHscs a confined, ovanescent field at the tip apex to conduct optical characterisation of a surface at length-scales below the diffraction limit. This thesis details the development of a new TER.S system based upon a shear-force scanning probe microscope (SPM) which sits atop an inverted microscope configured for bottom illumination geometry and coupled to a Raman spectrometer. The system has been optimised for use with solid silver probes and 532 nm illumination. Measurement procedures, automated scripts and data analysis software have been developed that allow reliable alignment of the tip; complex automated mapped measurements; and post processing which produces visual summary sheets to facilitate rapid review of a TERS experiment. Enhanced TERS spectra have been demonstrated on ultra-thin Rhodamine 6G films, self assembled monolayers (SAM) of thiophenole molecules, ultra-thin graphitic films and on multilayered graphene. Improvements in fabrication and alignment procedures have reduced the setup time between fabrication and approach to 20 minutes and improved the reliability of TERS tips with ~ 50% of tips demonstrating TERS activity. Using TERS, heightened defect sensitivity was observed on graphene edges, folds and overlapping regions. The TERS contrast of the defect induced D band was ~ 7.5 times the contrast of the graphene G band. Calculations show that the phonons correlating to the D and G bands interact differently with the enhanced TERS field and that the for certain defect types the D band experiences greater enhancement. Defects play an important role in tailoring the electronic and chemical properties of graphene which is key to the development of graphene based devices. The localised structural and spectral information makes TERS a highly promising tool for the characterisation of defects in graphene. This work demonstrates the potential of TERS for this exciting and important application.
published_date 2013-12-31T03:53:15Z
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score 11.013371

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