Photothermoelastic contrast in nanoscale infrared spectroscopy

Morozovska, Anna N.; Eliseev, Eugene A.; Borodinov, Nikolay; Ovchinnikova, Olga S.; Morozovsky, Nicholas V.; Kalinin, Sergei V.

doi:10.1063/1.4985584

Cited by 10 publications

(28 citation statements)

References 44 publications

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“…Morozovska et al propose that the width of such a step (δw) is the limiting factor for spatial resolution of photothermal measurements. 15 Their model predicts the frequency dependence of spatial resolution and provides values of δw that are qualitatively comparable to those expected in the thermal wave propagation limit by Bozec et al (Equation (1)). 14 It is interesting to examine the relationship between the spatial resolution of PTIR measurements and direct measurements of temperature increase in the sample.…”

Section: Spectromicroscopy Resolution and Thermal Wave Propagationsupporting

confidence: 65%

“…The bulk mechanical and thermal properties of PMMA and epoxy in our sample are similar or identical 15 and their variation is expected to provide a small or negligible contribution to the contrast observed in the images of Figure 3 and Figure 4. However, despite the homogenous bulk properties of the sample, some unexpected features are observed in the PTIR images in Figure 3.…”

Section: Imaging Resolutionmentioning

confidence: 54%

“…In the latter case the matrix expands with the object and resolution is limited by the extension of the expansion zone, as determined by the properties of the absorber. An expanded theoretical treatment by Morozovska et al 15 addresses the role of the thermoelastic properties of both absorber and embedding matrix on the geometry of photothermal expansion and their implications on spatial resolution. The latter model reveals a dependence of the modulation frequency on resolution, with higher frequency leading to improved resolution.…”

Section: Introductionmentioning

confidence: 99%

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Understanding and Controlling Spatial Resolution, Sensitivity, and Surface Selectivity in Resonant-Mode Photothermal-Induced Resonance Spectroscopy

Quaroni

2020

Anal. Chem.

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Photothermal-Induced Resonance (PTIR) is increasingly used in the measurement of infrared absorption spectra of sub-micrometer objects. The technique measures IR absorption spectra by relying on the photothermal effect induced by a rapid pulse of light and the excitation of the resonance spectrum of an AFM cantilever in contact with the sample. In this work we assess the spatial resolution and depth response of PTIR in resonant mode while systematically varying the pulsing frequency of the excitation laser and the cantilever resonance. The spatial resolution shows a shallow linear dependence on the inverse of the pulse frequency, which rules out tip size as a limiting factor for resolution in the frequency range under investigation. Measured resolution values are also one order of magnitude lower than in the thermal diffusion limit, excluding thermal wave propagation as a limiting factor. We also show that the pulsing frequency of the laser and choice of cantilever resonance affect the intensity of the signal and the surface selectivity in PTIR images, with higher frequencies providing increased surface selectivity. The results confirm a difference in signal generation between resonant PTIR and other photothermal techniques and indicate that photothermal induced heating and expansion cannot fully account for observed intensity and resolution.

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Section: Spectromicroscopy Resolution and Thermal Wave Propagationsupporting

confidence: 65%

Section: Imaging Resolutionmentioning

confidence: 54%

Section: Introductionmentioning

confidence: 99%

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Understanding and Controlling Spatial Resolution, Sensitivity, and Surface Selectivity in Resonant-Mode Photothermal-Induced Resonance Spectroscopy

Quaroni

2020

Anal. Chem.

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“…Recently, atomic force microscopy-based nanoscale infrared spectroscopy (AFM-IR), for which the highest spatial resolution of 10 nm can be achieved, was developed by Dazzi et al. 21–24 and has been applied to various types of systems 21–47 including polymer-metal interfaces. 26–31 The AFM-IR utilizes a sharp AFM probe with a typical tip radius of several tens of nanometers to detect local photothermal expansion of a sample surface induced by absorption of infrared (IR) irradiation, and its spatial resolution depends on the thermal expansion area detected by the apex of an AFM probe tip.…”

Section: Introductionmentioning

confidence: 99%

“…(ii) The spatial resolution depends not only on the tip size but also on the sample thermomechanical properties which will become dominant for thick samples and can deteriorate the lateral spatial resolution. 24,25 (iii) A theoretical result is also reported that the spatial resolution possibly deteriorates when the thermal conductivity of a substrate is lower or a sample is thicker, 38 although the model does not reproduce the rapid impulsive excitation in AFM-IR. (iv) Thin samples are also advantageous for quantitative measurements.…”

Section: Introductionmentioning

confidence: 99%

Novel Method for High-Spatial-Resolution Chemical Analysis of Buried Polymer-Metal Interface: Atomic Force Microscopy-Infrared (AFM-IR) Spectroscopy with Low-Angle Microtomy

Baden

2021

Appl Spectrosc

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There is a great need for the analysis of the chemical composition, structure, functional groups and interactions at polymerâmetal interfaces in terms of adhesion, corrosion, and insulation. Although atomic-force-microscopy-based infrared spectroscopy (AFM-IR) can provides chemical analysis with nanoscale spatial resolution, it generally requires to thin a sample to be placed on a substrate that has low absorption of infrared light and high thermal conductivity, which is often difficult for samples that contain hard materials like metals. This study demonstrates that the combination of AFM-IR with low-angle microtomy (LAM) sample-preparation can analyze buried polymerâmetal interfaces with higher spatial resolution than that with the conventional sample-preparation of a thick vertical cross-section. In the LAM of a polymer layer on a metal substrate, the polymer layer is tapered to be thin in the vicinity of the interface, and thus, sample thinning is not required. An interface between an epoxyacrylate layer and copper wire in a flexible printed circuit cable was measured using this method. A carboxylate interphase layer with a thickness of ~130 nm was clearly visualized at the interface, and its spectrum was obtained without any signal contamination from the neighboring epoxyacrylate, which was difficult to achieve on a thick vertical cross-section. The combination of AFM-IR with LAM is a simple and useful method for high-spatial-resolution chemical analysis of buried polymerâmetal interfaces.

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Micro to Nano: Multiscale IR Analyses Reveal Zinc Soap Heterogeneity in a 19th-Century Painting by Corot

Pavlidis

Dillon

et al. 2022

Anal. Chem.

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Formation and aggregation of metal carboxylates (metal soaps) can degrade the appearance and integrity of oil paints, challenging efforts to conserve painted works of art. Endeavors to understand the root cause of metal soap formation have been hampered by the limited spatial resolution of Fourier transform infrared microscopy (μ-FTIR). We overcome this limitation using optical photothermal infrared spectroscopy (O-PTIR) and photothermal-induced resonance (PTIR), two novel methods that provide IR spectra with ≈500 and ≈10 nm spatial resolutions, respectively. The distribution of chemical phases in thin sections from the top layer of a 19th-century painting is investigated at multiple scales (μ-FTIR ≈ 10 2 μm 3 , O-PTIR ≈ 10 −1 μm 3 , PTIR ≈ 10 −5 μm 3 ). The paint samples analyzed here are found to be mixtures of pigments (cobalt green, lead white), cured oil, and a rich array of intermixed, small (often ≪ 0.1 μm 3 ) zinc soap domains. We identify Zn stearate and Zn oleate crystalline soaps with characteristic narrow IR peaks (≈1530−1558 cm −1 ) and a heterogeneous, disordered, water-permeable, tetrahedral zinc soap phase, with a characteristic broad peak centered at ≈1596 cm −1 . We show that the high signal-to-noise ratio and spatial resolution afforded by O-PTIR are ideal for identifying phase-separated (or locally concentrated) species with low average concentration, while PTIR provides an unprecedented nanoscale view of distributions and associations of species in paint. This newly accessible nanocompositional information will advance our knowledge of chemical processes in oil paint and will stimulate new art conservation practices.

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Photothermoelastic contrast in nanoscale infrared spectroscopy

Cited by 10 publications

References 44 publications

Understanding and Controlling Spatial Resolution, Sensitivity, and Surface Selectivity in Resonant-Mode Photothermal-Induced Resonance Spectroscopy

Understanding and Controlling Spatial Resolution, Sensitivity, and Surface Selectivity in Resonant-Mode Photothermal-Induced Resonance Spectroscopy

Novel Method for High-Spatial-Resolution Chemical Analysis of Buried Polymer-Metal Interface: Atomic Force Microscopy-Infrared (AFM-IR) Spectroscopy with Low-Angle Microtomy

Micro to Nano: Multiscale IR Analyses Reveal Zinc Soap Heterogeneity in a 19th-Century Painting by Corot

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