Effect of hybrid field coupling in nanostructured surfaces on anisotropic signal detection in nanoscale infrared spectroscopic imaging methods

Ayona James; Maryam Ali; Zekai Ye; Phan Thi Yen Nhi; Sharon Xavi; Mashiat Huq; Sajib Barua; Meng Luo; Yisak Tsegazab; Anna Elmanova; Robin Schneider; Olga Ustimenko; Sarmiza-Elena Stanca; Marco Diegel; Andrea Dellith; Uwe Hübner; Christoph Krafft; Jasmin Finkelmeyer; Maximilian Hupfer; Kalina Peneva; Matthias Zeisberger; Christin David; Martin Presselt; Daniela Täuber

doi:10.1039/d6fd00003g

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arXiv · 2512.22373

Effect of hybrid field coupling in nanostructured surfaces on anisotropic signal detection in nanoscale infrared spectroscopic imaging methods

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Abstract

Anisotropic intensity distributions on nanostructured surfaces and polarization-sensitive spectra have been observed in a number of nanoscale infrared spectroscopic imaging methods, including nano-FTIR [Bakir et al., Molecules, 2020, 25, 4295], photothermal induced resonance (PTIR) [Waeytens et al., Analyst, 2021, 146], tapping AFM-IR [Hondl et al., ACS Meas. Sci. Au, 2025, 5, 469; Luo et al., APL, 2022, 121, 23330], infrared photoinduced force microscopy (PiF-IR) [Anindo et al., JPCC, 2025, 129, 4517; Shcherbakov et al., Rev Methods Primers, 2025, 5, 1; Ali et al., Anal. Chem., 2025, 97, 23914] and peak force infrared microscopy (PFIR) [Xie et al., JPCC, 2022, 126, 8393; Anindo, JPCC, 2025]. A recent work combining modeling and experiment demonstrated that the hybrid field coupling of the IR illumination E0 with a polymer nanosphere and a metallic AFM probe is nearly as strong as the plasmonic coupling in case of a gold nanosphere [Anindo, JPCC, 2025]. For p-polarized illumination, this results in enhanced IR absorption on the surface perpendicular to the propagation of E0 which can explain the observed anisotropic intensity distribution. An additional anisotropy may be introduced by aligned surface molecules with oriented vibrational transition moments [Bakir et al., Molecules, 2020, 25, 4295; Luo, APL, 2022]. PiF-IR is strongly surface sensitive combining an unprecedented spatial resolution < 5 nm with high spectral resolution [Shcherbakov, Rev Methods Primers, 2025; Ali, Anal. Chem., 2025], which allows, for example, to visualize nanoscale chemical variation on the surface of bacteria cells affected by antimicrobial interaction [Ali, Anal. Chem., 2025]. We compare PiF-IR hyperspectra of aligned perylene Langmuir Blodgett monolayers on nanostructured and planar gold substrates and use quantum chemical calculations of the oriented vibrational oscillators to interpret the observations.

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Ayona James, Maryam Ali, Zekai Ye, Phan Thi Yen Nhi, Sharon Xavi, Mashiat Huq, Sajib Barua, Meng Luo, Yisak Tsegazab, Anna Elmanova, Robin Schneider, Olga Ustimenko, Sarmiza-Elena Stanca, Marco Diegel, Andrea Dellith, Uwe Hübner, Christoph Krafft, Jasmin Finkelmeyer, Maximilian Hupfer, Kalina Peneva, Matthias Zeisberger, Christin David, Martin Presselt, Daniela Täuber. 2025-12-26. Effect of hybrid field coupling in nanostructured surfaces on anisotropic signal detection in nanoscale infrared spectroscopic imaging methods. https://doi.org/10.1039/d6fd00003g

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