Infrared vibrational nanocrystallography and nanoimaging

Muller, Eric A.; Pollard, Benjamin; Bechtel, Hans A.; Blerkom, Peter van; Raschke, Markus B.

doi:10.1126/sciadv.1601006

Cited by 64 publications

(63 citation statements)

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confidence: 91%

“…We show nanoscale maps of crystallographic structure in molecular materials through characteristic normal modes using IR s-SNOM. We observe nanoscale defects through spatial variation in the molecular orientation of otherwise morphologically well-ordered thin films [3].Through vibrational solvatochromism, IR s-SNOM gives insight into coupled electronic structure, local electric fields, and charge transfer. Vibrational resonances can shift in frequency or change in line width due to modifications in their local chemical environment.…”

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confidence: 96%

“…Together with the associated enhanced near-field light-matter interaction based on improved mode matching provides domain-level structural information and even single-molecule sensitivity. We present several recent advances in near-field microscopy applied to nanoscale chemical identification, imaging nanoscale defects and the local chemical environment, and observations of dynamical fluctuations at the single molecule limit [1][2][3][4][5].IR s-SNOM has become a powerful tool for nanoscale chemical identification of organic materials. Selected single wavelength IR s-SNOM tuned to the frequency of a characteristic vibrational mode has become a routine method for chemical mapping with nanoscale resolution, while broadband IR s-SNOM can offer greater chemical information through spectroscopic analysis of one or more vibrational modes (Fig.…”

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confidence: 99%

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confidence: 99%

“…[1]. b) SINS and IR s-SNOM measure crystallinity and image orientational defects in a thin film molecular material [2][3]. c) TERS time series spectra measure intramolecular vibrational redistribution and single molecule spectra diffusion [5].…”

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Chemical Nano-Imaging with Tip-Enhanced Vibrational Spectroscopy

Muller

Raschke

2017

Microsc Microanal

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Many organic materials in electronic biological systems gain functionality through molecular structuring, heterogeneous morphologies, chemical interactions and coupling at functional interfaces. A major obstacle to understanding the fundamental nature of intra-inter-molecular interactions, however, is the combination of multi-length scale structural disorder ranging from nanometers to micrometers and multi-timescale dynamical interactions ranging from femtoseconds to minutes.To gain the desired nanometer spatial resolution with simultaneous spectroscopic specificity we combine scanning probe microscopy with vibrational spectroscopies using both tip-enhanced Raman (TER) and IR scattering scanning near-field optical microscopy (IR s-SNOM). We use TERS and IR s-SNOM to probe at the homogeneous sample size limit by virtue of the nanometer spatial near-field localization. Together with the associated enhanced near-field light-matter interaction based on improved mode matching provides domain-level structural information and even single-molecule sensitivity. We present several recent advances in near-field microscopy applied to nanoscale chemical identification, imaging nanoscale defects and the local chemical environment, and observations of dynamical fluctuations at the single molecule limit [1][2][3][4][5].IR s-SNOM has become a powerful tool for nanoscale chemical identification of organic materials. Selected single wavelength IR s-SNOM tuned to the frequency of a characteristic vibrational mode has become a routine method for chemical mapping with nanoscale resolution, while broadband IR s-SNOM can offer greater chemical information through spectroscopic analysis of one or more vibrational modes (Fig. 1A). Using synchrotron infrared nano-spectroscopy (SINS) we extend the spectral range to ultrabroadband nanoscale spectroscopy spanning 300-5000 cm -1 to provide unambiguous nanoscale chemical identification through the vibrational fingerprint [2].We show an extension of infrared nano-spectroscopy to investigate the structure-function relationship of materials beyond basic chemical identity, using the structural sensitivity of vibrational modes combined with nanoscale spatial resolution. The sensitivity to bond orientation and packing gives access to measures of disorder, structural orientation, and polymorphism. From the symmetry-selective probing of vibrational normal modes we determine phases and orientation in aggregates and thin films of a molecular semiconductor as shown in Fig. 1B. We show nanoscale maps of crystallographic structure in molecular materials through characteristic normal modes using IR s-SNOM. We observe nanoscale defects through spatial variation in the molecular orientation of otherwise morphologically well-ordered thin films [3].Through vibrational solvatochromism, IR s-SNOM gives insight into coupled electronic structure, local electric fields, and charge transfer. Vibrational resonances can shift in frequency or change in line width due to modifications in their local chemical environment....

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confidence: 91%

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confidence: 96%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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Chemical Nano-Imaging with Tip-Enhanced Vibrational Spectroscopy

Muller

Raschke

2017

Microsc Microanal

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Exploiting Phonon‐Resonant Near‐Field Interaction for the Nanoscale Investigation of Extended Defects

Hauer

Marvinney

Lewin

et al. 2020

Adv Funct Materials

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The evolution of wide bandgap semiconductor materials has led to dramatic improvements for electronic applications at high powers and temperatures. However, the propensity of extended defects provides significant challenges for implementing these materials in commercial electronic and optical applications. While a range of spectroscopic and microscopic tools have been developed for identifying and characterizing these defects, such techniques typically offer either technique exclusively, and/or may be destructive. Scattering‐type scanning near‐field optical microscopy (s‐SNOM) is a nondestructive method capable of simultaneously collecting topographic and spectroscopic information with frequency‐independent nanoscale spatial precision (≈20 nm). Here, how extended defects within 4H‐SiC manifest in the infrared phonon response using s‐SNOM is investigated and the response with UV‐photoluminescence, secondary electron and electron channeling contrast imaging, and transmission electron microscopy is correlated. The s‐SNOM technique identifies evidence of step‐bunching, recombination‐induced stacking faults, and threading screw dislocations, and demonstrates interaction of surface phonon polaritons with extended defects. The results demonstrate that phonon‐enhanced infrared nanospectroscopy and spatial mapping via s‐SNOM provide a complementary, nondestructive technique offering significant insights into extended defects within emerging semiconductor materials and devices and thus serves as an important diagnostic tool to help advance material growth efforts for electronic, photonic, phononic, and quantum optical applications.

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In Situ Infrared Micro and Nanospectroscopy for Discharge Chemical Composition Investigation of Non‐Aqueous Lithium–Air Cells

Nepel

Anchieta

Cremasco

et al. 2021

Advanced Energy Materials

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Metal–air batteries, such as Li–air, may be the key for large‐scale energy storage as they have the highest energy density among all electrochemical devices. However, these devices suffer from irreversible side reactions leading to battery failure, especially when ambient air is used as the O2 source, so a deep understanding over the surface chemistry evolution is imperative for building better devices. Herein, a multi‐scale (nano‐micro) FTIR analysis is made over the electrode surface during cell discharge employing synchrotron infrared nanospectroscopy (SINS) for the first time, to track the chemical composition changes at the nanoscale which are successfully correlated with in operando micro‐FTIR characterization. The in situ results reveal homogeneous product distribution from the nano to the micro scale, and that the discharge rate does not interfere in chemical composition. In operando micro‐FTIR shows the atmosphere dependency over Li products formation; the presence of HCOO– species occurring due to CO2 electroreduction in water, LiOH and Li2CO3, are also detected and even the lowest concentration of CO2 and H2O affects the O2 reactions. Finally, evidence of the Li2O2 reaction with DMSO forming DMSO2 after just 140 s of cell discharge shows this new technique's relevance in aiding the search for stable electrolytes.

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Infrared vibrational nanocrystallography and nanoimaging

Abstract: Nanoscale spectroscopy and imaging of organic materials reveal heterogeneity in molecular orientation in crystalline domains.

Cited by 64 publications

References 44 publications

Chemical Nano-Imaging with Tip-Enhanced Vibrational Spectroscopy

Chemical Nano-Imaging with Tip-Enhanced Vibrational Spectroscopy

Exploiting Phonon‐Resonant Near‐Field Interaction for the Nanoscale Investigation of Extended Defects

In Situ Infrared Micro and Nanospectroscopy for Discharge Chemical Composition Investigation of Non‐Aqueous Lithium–Air Cells

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