Local infrared microspectroscopy with subwavelength spatial resolution with an atomic force microscope tip used as a photothermal sensor

Dazzi, Alexandre; Prazérès, R.; Glotin, F.; Ortéga, J.M.

doi:10.1364/ol.30.002388

Cited by 336 publications

(292 citation statements)

References 13 publications

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“…After several years of work in near-field IR optics with these different techniques, we developed, with our coworkers, another m ethod based on photothermal-induced absorption. The technique, called atomic force microscopy (AFM)-IR, 19 irradiates a region of a sample with light from a tunable IR laser and measures the resulting photothermal expansion of the sample with the tip of an atomic force microscope. The first experimental setup was established in the Centre Laser Infrarouge d'Orsay (CLIO) in the Laboratoire de Chimie Physique by using a free-electron laser as the tunable IR source.…”

Section: Introductionmentioning

confidence: 99%

AFM–IR: Combining Atomic Force Microscopy and Infrared Spectroscopy for Nanoscale Chemical Characterization

Dazzi

Prater²,

Hu³

et al. 2012

Appl Spectrosc

467

444

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Polymer and life science applications of a technique that combines atomic force microscopy (AFM) and infrared (IR) spectroscopy to obtain nanoscale IR spectra and images are reviewed. The AFM–IR spectra generated from this technique contain the same information with respect to molecular structure as conventional IR spectroscopy measurements, allowing significant leverage of existing expertise in IR spectroscopy. The AFM–IR technique can be used to acquire IR absorption spectra and absorption images with spatial resolution on the 50 to 100 nm scale, versus the scale of many micrometers or more for conventional IR spectroscopy. In the life sciences, experiments have demonstrated the capacity to perform chemical spectroscopy at the sub-cellular level. Specifically, the AFM–IR technique provides a label-free method for mapping IR-absorbing species in biological materials. On the polymer side, AFM–IR was used to map the IR absorption properties of polymer blends, multilayer films, thin films for active devices such as organic photovoltaics, microdomains in a semicrystalline polyhydroxyalkanoate copolymer, as well as model pharmaceutical blend systems. The ability to obtain spatially resolved IR spectra as well as high-resolution chemical images collected at specific IR wavenumbers was demonstrated. Complementary measurements mapping variations in sample stiffness were also obtained by tracking changes in the cantilever contact resonance frequency. Finally, it was shown that by taking advantage of the ability to arbitrarily control the polarization direction of the IR excitation laser, it is possible to obtain important information regarding molecular orientation in electrospun nanofibers.

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Section: Introductionmentioning

confidence: 99%

AFM–IR: Combining Atomic Force Microscopy and Infrared Spectroscopy for Nanoscale Chemical Characterization

Dazzi

Prater²,

Hu³

et al. 2012

Appl Spectrosc

467

444

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show abstract

“…The TEIRA phenomenon can be achieved by the use of IR spectroscopy combined with atomic force microscopy (AFM-IR) [16,18,19]. The AFM-IR technique incorporates all features and advantages that are supplied by AFM and IR separately [20].…”

Section: Introductionmentioning

confidence: 99%

Polarization effect in tip-enhanced infrared nanospectroscopy studies of the selective Y5 receptor antagonist Lu AA33810

et al. 2018

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A novel approach of combining conventional infrared spectroscopy (IR) and atomic force microscopy (AFM) is presented to better understand the behavior of a drug adsorbed on a metal substrate at the nanoscale level. Tip-enhanced infrared nanospectroscopy (TEIRA) was used for the first time to investigate Lu AA33810, a selective brain-penetrating Y5 receptor antagonist, after immobilization on gold nanoparticles (GNPs). Here, a gold coated AFM tip and gold substrate were used to obtain the near-field electromagnetic field trapping effect. Because of the huge signal enhancement, it was possible to obtain the spectral information regarding the self-assembled monolayer of the investigated molecule. The effect of two orthogonal polarizations (p-and s-polarization modulations) of the excitation laser beam on the spectral patterns is also discussed. The results show that there is a strong relationship between the state of polarization of the incident radiation and the relative infrared band intensities. Another factor affecting the observed spectral differences is the topology of the metal substrate, which may result in the induction of a cross-polarization effect. The performed analysis indicates that the C-C bond from the cyclohexyl group is oriented almost parallel to the metal surface. Conversely, the p-and s-polarized spectral variations suggest that the O=S=O angle is high enough to enable the simultaneous interaction of both oxygen atoms with the GNPs.

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“…More recently a top-down version of the system was commercialized (NanoIR2 in 2013). The AFM-IR method relies on detection of IR absorption under the AFM tip by rapid photothermal expansion [9,10]. Such an approach breaks the diffraction limit enabling IR mapping at <50 nm spatial resolution exceeding that of confocal Raman by 10X and FTIR by 100X [11].…”

mentioning

confidence: 99%

Atomic Force Microscopy of Polymer Systems: From Morphology to Properties to Chemical Imaging and Spectroscopy

Meyers

2016

Microsc Microanal

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Scanned probe microscopy (SPM) has had a long history at The Dow Chemical Company, beginning in the late 1980s when commercial scanning tunneling microscopes were just hitting the market. Since that time Dow has invested in internal and external collaborative efforts to drive and develop atomic force based technologies for property measurements of polymeric materials at nanometer length scales. The vision of SPM as truly a "lab on a tip" [1] for nanoscale materials research is a key driver for our efforts.Our most cited early work described a unique phenomenon of surface wear of polystyrene thin films where the interaction of a sliding AFM tip lead to characteristic patterns that depended on the polymer molecular weight [2]. Since that time work such as this has been studied in order to understand elastic, adhesive, and thermal properties of polymer coatings and films near rigid interfaces. Collaborations with NIST in the late 1990s provided our first attempts at quantifying mechanical properties at the nanoscale, combining knowledge gained from classical nanoindentation to the calibration of AFM systems for quantitative AFM based indentation [3,4]. This work set the stage for a large scale effort in the latter 2000 time frame, funded by the NIST-ATP program in collaboration with Veeco Instruments (now Bruker-Nano). The objective of this program was to develop an AFM based platform for quantitative modulus measurements of polymers at sub 100 nm length scales, to provide better than 10% precision for polymer materials with bulk properties in the 10 MPa to 10 GPa range. As a result of this program, we now have quasistatic AFM based indentation capability that provides the most comprehensive suite of analytical models (elastic, elastic-plastic, and adhesive) to interpret material properties at these scales [5]. Within the last few years the ability to map properties at high spatial resolution via high speed AFM indenting has been realized [6]. A key consideration in all of the mechanical probing is the time scale over which the tip-surface interaction occurs and so we have looked to computational simulations with Purdue University to study the role of dissipative factorsviscoelasticity and surface adhesion hysteresis -to help interpret our measurements.Concurrent with these developments has been our interest in both measuring and mapping thermal properties of polymer materials using heated AFM probe technology. The transition from micron to nanoscale measurements will be described [7,8].From 2008-2010 Dow worked with Anasys Instruments on the development of an AFM-infrared (IR) capability (commercialized as the NanoIR in 2010). More recently a top-down version of the system was commercialized (NanoIR2 in 2013). The AFM-IR method relies on detection of IR absorption under the AFM tip by rapid photothermal expansion [9,10]. Such an approach breaks the diffraction limit enabling IR mapping at <50 nm spatial resolution exceeding that of confocal Raman by 10X and FTIR by 100X [11]. The method now allows us to 'see' wher...

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Local infrared microspectroscopy with subwavelength spatial resolution with an atomic force microscope tip used as a photothermal sensor

Cited by 336 publications

References 13 publications

AFM–IR: Combining Atomic Force Microscopy and Infrared Spectroscopy for Nanoscale Chemical Characterization

AFM–IR: Combining Atomic Force Microscopy and Infrared Spectroscopy for Nanoscale Chemical Characterization

Polarization effect in tip-enhanced infrared nanospectroscopy studies of the selective Y5 receptor antagonist Lu AA33810

Atomic Force Microscopy of Polymer Systems: From Morphology to Properties to Chemical Imaging and Spectroscopy

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