Nanoscale-resolved chemical identification of thin organic films using infrared near-field spectroscopy and standard Fourier transform infrared references

Mastel, Stefan; Govyadinov, Alexander A.; Oliveira, Thales V. A. G. de; Amenabar, Ibán; Hillenbrand, Rainer

doi:10.1063/1.4905507

Cited by 106 publications

(108 citation statements)

References 31 publications

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“…For relatively thick samples, it is generally accepted that the absorption is proportional to the imaginary component of the scattered field, A sin φ, 22,23 where A is the optical amplitude and φ is the local phase difference relative to the incident field. The aNSOM is configured as a pseudoheterodyne Michelson interferometer in order to extract the optical phase.…”

mentioning

confidence: 99%

Near-Field IR Nanoscale Imaging of the Solid Electrolyte Interphase on a HOPG Electrode

Ayache

Jang

Syzdek

et al. 2015

J. Electrochem. Soc.

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The SEI layer on graphitic carbon electrodes is well known to protect effectively the electrode from further electrolyte reduction during long-term charge-discharge cycling process. Many different techniques have been applied to characterize the chemical and structural composition of this complex surface film. The standard vibrational optical spectroscopies, which offer molecular-level information are subject to the diffraction limit, which restricts their ability to probe at the nanoscale level of the SEI building blocks. This work exploits infrared apertureless near-field microscopy that operates below the diffraction limit to characterize the SEI layer on a model HOPG electrode. Variations in surface topography and chemical contrast are discussed in the context of SEI composition and function. The solid electrolyte interphase (SEI) layer is integral to the functionality of Li-ion battery cells.1,2 It consists of products of cathodic reduction of the electrolyte at the negative electrode, which in stable battery systems is a self-limiting process.3 The SEI layer's stability determines Li-ion battery longevity, electrochemical performance and safety. By contrast, in unstable systems besides poor passivating properties and/or gradual dissolution, the SEI can be broken up by volumetric changes of the electrode active material during lithiation/delithiation. These detrimental phenomena cause the SEI to (re)grow continuously and/or reform during battery cycling, consuming the electrolyte, raising electrode impedance, shifting lithium inventory in the cell and reducing cell discharge capacity.Understanding what chemical components perform the key structural and chemical roles in functional SEI layers is prerequisite to the ability of stabilizing Li-ion electrodes that operate outside of the window of stability of the organic electrolyte. Numerous attempts have been made to characterize the structure and chemical composition of the SEI, involving a vast array of techniques, including but not limited to Fourier transform infrared spectroscopy (FTIR), 4 atomic force microscopy (AFM), 5,6 scanning electron microscopy (SEM), 7 X-ray techniques such as X-ray photoelectron spectroscopy (XPS) 8 and X-ray absorption spectroscopy (XAS), 9 Raman spectroscopy and microscopy, 10,11 and fluorescence spectroscopy. 12 Vibrational spectroscopies such as FTIR and Raman are particularly useful for the characterization of structures and molecular bonds to reconstruct the identity of chemical compounds in the layer.However, the spatial resolution of standard optical spectroscopic and imaging techniques is limited by diffraction to light beam sizes on the order of the wavelength of the source i.e., ∼10 μm for IR and ∼500 nm in the visible range. This often implies a lack of surface sensitivity, low spatial resolution in imaging, and spectral convolution in spectroscopy. Therefore a typical FTIR spectrum of an SEI layer consists of a multitude of overlapping peaks, which are difficult to deconvolute into independent spectra of constituent...

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confidence: 99%

Near-Field IR Nanoscale Imaging of the Solid Electrolyte Interphase on a HOPG Electrode

Ayache

Jang

Syzdek

et al. 2015

J. Electrochem. Soc.

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“…For an SiO 2 film on Si, calculations that approximate the tip as a spheroid of length 2L and radius r (r ) are often used to quantify the relative amounts of chemical species in a mixture via multivariate analysis. Although experimental validation on heterogeneous samples is needed, significant progress in relating s-SNOM spectra with far-field FTIR spectra was recently accomplished through analyses of the amplitude (A), phase, and absorption (A abs = |A|sinΦ) signals as a function of thickness in PMMA films on highly reflective substrates (Si) (102). Peak intensities in the phase spectra increased with thickness, and their positions (blue-shifted by ≈3 and 9 cm −1 with respect to far-field grazing angle and transmission spectra, respectively) are mostly insensitive to the thickness.…”

Section: Scattering Scanning Near-field Optical Microscopymentioning

confidence: 99%

Infrared Imaging and Spectroscopy Beyond the Diffraction Limit

Centrone

2015

Annual Rev. Anal. Chem.

243

275

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Progress in nanotechnology is enabled by and dependent on the availability of measurement methods with spatial resolution commensurate with nanomaterials' length scales. Chemical imaging techniques, such as scattering scanning near-field optical microscopy (s-SNOM) and photothermal-induced resonance (PTIR), have provided scientists with means of extracting rich chemical and structural information with nanoscale resolution. This review presents some basics of infrared spectroscopy and microscopy, followed by detailed descriptions of s-SNOM and PTIR working principles. Nanoscale spectra are compared with far-field macroscale spectra, which are widely used for chemical identification. Selected examples illustrate either technical aspects of the measurements or applications in materials science. Central to this review is the ability to record nanoscale infrared spectra because, although chemical maps enable immediate visualization, the spectra provide information to interpret the images and characterize the sample. The growing breadth of nanomaterials and biological applications suggest rapid growth for this field.

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“…All spectral data had a zero-fill factor of 4, so that the final spectra were saved at a nominal spectral resolution of 2.1 cm -1 . Please do not adjust margins Please do not adjust margins spatial resolution from the complex-valued second order scattering coefficient, (σ 2 ), [26][27][28] given by equation 1:…”

Section: Sins Spectral Collectionmentioning

confidence: 99%

Ultrastructural and SINS analysis of the cell wall integrity response ofAspergillus nidulansto the absence of galactofuranose

Bakir

Girouard

Johns

et al. 2019

Analyst

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Nanoscale-resolved chemical identification of thin organic films using infrared near-field spectroscopy and standard Fourier transform infrared references

Cited by 106 publications

References 31 publications

Near-Field IR Nanoscale Imaging of the Solid Electrolyte Interphase on a HOPG Electrode

Near-Field IR Nanoscale Imaging of the Solid Electrolyte Interphase on a HOPG Electrode

Infrared Imaging and Spectroscopy Beyond the Diffraction Limit

Ultrastructural and SINS analysis of the cell wall integrity response ofAspergillus nidulansto the absence of galactofuranose

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