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Evading the Illusions: Identification of False Peaks in Raman Spectroscopy and Guidelines for Appropriate Measurement Protocols.
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solid State Physics.ORCID iD: 0000-0002-9812-7370
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solid State Physics.ORCID iD: 0000-0003-2759-7356
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Raman spectroscopy is an important analytical tool in materials science. Its ability to characterize transitions between rotational and vibrational states by analysis of inelastically scattered light, enables it to identify chemical bonds. As changes of the rotational and vibrational states in turn depend on secondary effects, the technique is also suitable for studying more detailed phenomena like molecular interactions, material strain, crystallinity, order and bond formations. This versatility has made it a standard tool in a large variety of science disciplines including chemistry, physics, biology, geology and medicine. There are several advantages with Raman spectroscopy including that it in most cases is non-destructive, requires no sample preparation and that almost any non-metallic type of sample can be measured. Raman scattering has however one major weakness: It is a very low probability process unless probed in resonance with an electronic excitation. To detect such a weak signal at a high spectral resolution, a very sensitive detection system is needed which subsequently leads to a high probability of picking up signal from other processes or from other origin than the measured sample. These spurious signals that sometimes occur in Raman spectra are referred to as false Raman peaks and if they are not correctly identified, they complicate the analysis of the results and increase the risk of misinterpreting the data. This work is aimed to give the fundamental principles of Raman scattering and an overview of the sources of other signals occurring in Raman spectra that include; other photon generating processes, cosmic rays, stray light, artefacts from spectrometer components, and signals from other compounds in or surrounding the sample. The origins of the false Raman peaks are explained and means and measures to identify and counteract them are given. Finally, a Raman measurement protocol that can serve as a guideline for practical confocal Raman spectroscopy measurements is presented.

Keywords [en]
Raman spectroscopy, Spectral artifacts, Measurement protocol
National Category
Materials Engineering Atom and Molecular Physics and Optics
Research subject
Engineering Science with specialization in Solid State Physics; Engineering Science with specialization in Solid State Physics; Engineering Science with specialization in Solid State Physics
Identifiers
URN: urn:nbn:se:uu:diva-486413OAI: oai:DiVA.org:uu-486413DiVA, id: diva2:1701797
Available from: 2022-10-07 Created: 2022-10-07 Last updated: 2022-10-09
In thesis
1. Low dimensional Zinc- and Copper Oxides and their Electronic, Vibrational and Photocatalytic Properties
Open this publication in new window or tab >>Low dimensional Zinc- and Copper Oxides and their Electronic, Vibrational and Photocatalytic Properties
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Pollution of water resources is a growing problem in the world and this has drawn the attention to photocatalysis, which is an emerging technology for water purification. In this thesis, low dimensional zinc oxide and copper oxides, which are promising photocatalytic materials, have been studied. In the initial work, an approach for determining the crystal orientation in ZnO nanomaterials was developed based on polarized Raman spectroscopy. The approach was extended to non-polarized Raman spectroscopy for convenient crystal orientation determination. The results were corroborated by density functional theory (DFT) calculations providing a full vibrational mode analysis of ZnO, including higher-order Raman scattering. Photocatalyst materials based on both ZnO and copper oxides were synthesized, starting with visible light absorbing Cu2O prepared by low temperature thermal oxidation of flat and 3D structured Cu-foils. Defect induced Raman scattering revealed Raman activity in modes that are only IR active or optically silent in pristine Cu2O, with mode assignments supported by DFT calculations. Experiment with solar light illuminated Cu2O showed efficient degradation of organic water-soluble molecules and degradation rates could be further increased by 3D structuring into nanopillars. With the aim of creating a combined photocatalyst that use favourable properties from several materials, nanoparticles of ZnO were synthesized and deposited onto Cu2O, Cu4O3 and CuO. ZnO of sufficiently small size exhibit quantum confinement, which allowed for tuning of the electronic and optical properties of ZnO and this was utilized for energy level alignment in heterojunctions with copper oxides. The heterojunctions were shown to facilitate charge transfer which improved the photocatalytic properties of the dual catalysts compared to the single components. The quantum confinement effects in ZnO nanoparticles were further investigated by more detailed electrochemical measurements. The main finding was that quantum confinement results in a large decrease in the available electronic density of states which has clear implications on the capacitance and photon absorption in the material. Raman spectroscopy has been a central tool in all work, and the thesis ends with a study that goes through and explain spurious Raman signals. The contribution shows how to identify and avoid spectral artefacts and other light generating processes that compete with the Raman signal and guide the acquisition of good quality spectra.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2022. p. 103
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2199
Keywords
ZnO, Cu2O, CuO, Cu4O3, Photocatalysis, Raman spectroscopy, Nano materials, Quantum confinement, Quantum dots, Size dependent properties, Crystal orientation, Density functional theory
National Category
Materials Engineering
Research subject
Engineering Science with specialization in Solid State Physics
Identifiers
urn:nbn:se:uu:diva-486457 (URN)978-91-513-1620-8 (ISBN)
Public defence
2022-11-25, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2022-11-01 Created: 2022-10-09 Last updated: 2022-12-12

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Thyr, JakobEdvinsson, Tomas

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