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Single layer graphene for estimation of axial spatial resolution in confocal Raman microscopy depth profiling

DOI:10.1021/acs.analchem.8b04390 期刊:Analytical Chemistry 出版年份:2018 更新时间:2025-09-04 15:30:14
摘要: Single layer graphene (SLG), with its angstrom-scale thickness and strong Raman scattering cross section, was adapted for measurement of the axial (Z-direction) probe beam profile in confocal Raman microscopy depth-profiling experiments. SLG adsorbed to a glass microscope coverslip (SLG/SiO2) served as a platform for estimation of axial spatial resolution. Profiles were measured by stepping the confocal probe volume through the SLG/SiO2 interface while measuring Raman scattering from the sample. Using a high numerical aperture (1.4 NA) oil immersion objective, axial profiles were derived from the graphene 2D vibrational mode and fit to a Lorentzian instrument response function (IRF). Subsequently, the Z-direction spatial resolution in depth-profiling studies of polymer interfaces was estimated through convolution of the Lorentzian IRF with a step function representing the ideal junction separating the phases of interest. In the study of a bipolar polymer membrane, confocal Raman depth profiles of the AEM/CEM (anion exchange membrane / cation exchange membrane) interface show the transition region is broader than the limiting response and are consistent with roughness at the boundary on the order of a few micrometers. Using ClO4- as a Raman active mobile ion probe, application of self-modeling curve resolution (SMCR) to spectral datasets within a profile showed ClO4- ions track the spatial distribution of the AEM phase. Finally, in measurements on a liquid-solid interface formed between 1-octanol and a polydimethylsiloxane (PDMS) membrane, the IRF derived from fitting the experimental profile was slightly narrower than those obtained from profiling SLG, indicating the potential to use polymer-liquid interfaces formed from widely available materials and reagents for estimation of axial spatial resolution in confocal Raman depth-profiling.
作者: Carol Korzeniewski,Jay P. Kitt,Saheed Bukola,Stephen E. Creager,Shelley D. Minteer,Joel M. Harris
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To measure the axial (Z-direction) probe beam profile in confocal Raman microscopy depth-profiling experiments using single layer graphene (SLG) and to estimate the axial spatial resolution for studies of polymer interfaces.

The study demonstrated that SLG is a sensitive platform for measuring the axial probe volume detection efficiency profile in confocal Raman microscopy. The derived beam profile enables estimation of the limiting Z-direction spatial resolution for depth-profiling experiments. The method was successfully applied to study polymer interfaces and bipolar membranes, showing potential for guiding the design of next-generation membranes.

The study is limited by the technical constraints of confocal Raman microscopy, including refraction, spherical aberration, and stray scattering through the probe volume, which can degrade spatial resolution. Additionally, the method requires careful alignment and calibration to achieve accurate depth profiling.

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