4.8 Article

Photothermal Atomic Force Microscopy Coupled with InfraredSpectroscopy (AFM-IR) Analysis of High Extinction CoefficientMaterials: A Case Study with Silica and Silicate Glasses

Journal

ANALYTICAL CHEMISTRY
Volume 94, Issue 13, Pages 5231-5239

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.analchem.1c04398

Keywords

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Funding

  1. National Science Foundation [DMR-2011410]
  2. Center for Performance and Design of Nuclear Waste Forms and Containers, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0016584]
  3. Corning, Inc.

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Photothermal atomic force microscopy coupled with infrared spectroscopy (AFM-IR) is a valuable technique for surface analysis of disordered oxide materials. However, further development and understanding of the underlying principles are needed to interpret AFM-IR spectra. This paper presents theoretical calculations and discusses the differences between AFM-IR spectra and other spectra, as well as the information depth of AFM-IR characterization.
Photothermal atomic force microscopy coupledwith infrared spectroscopy (AFM-IR) brings significant value as aspatially resolved surface analysis technique for disordered oxidematerialssuchasglasses,butadditional development andfundamental understanding of governing principles is needed tointerpret AFM-IR spectra, since the existing theory described fororganic materials does not work for materials with high extinctioncoefficients for infrared (IR) absorption. This paper describestheoretical calculation of a transient temperature profile inside theIR-absorbing material considering IR refraction at the interface aswell as IR adsorption and heat transfer inside the sample. Thiscalculation explains the differences in peak positions andamplitudes of AFM-IR spectra from those of specular reflectanceand extinction coefficient spectra. It also addresses the information depth of the AFM-IR characterization of bulk materials. AFM-IRapplied to silica and silicate glass surfaces has demonstrated novel capability of characterizing subsurface structural changes andsurface heterogeneity due to mechanical stresses from physical contacts, as well as chemical alterations manifested in surface layersthrough aqueous corrosion.

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