Nanoscale Infrared Research Articles

Nanoscale Infrared Spectroscopy: Improving the Spectral Range of the Photothermal Induced Resonance Technique

Photothermal induced resonance (PTIR) is a new technique which combines the chemical specificity of infrared (IR) spectroscopy with the lateral resolution of atomic force microscopy (AFM). PTIR requires a pulsed tunable laser for sample excitation and an AFM tip to measure the sample expansion induced by light absorption. The limited tunability of commonly available laser sources constrains the application of the PTIR technique to a portion of the IR spectrum. In this work, a broadly tunable pulsed laser relying on a difference frequency generation scheme in a GaSe crystal to emit light tunable from 1.55 μm to 16 μm (from 6450 cm(-1) to 625 cm(-1)) was interfaced with a commercial PTIR instrument. The result is a materials characterization platform capable of chemical imaging, in registry with atomic force images, with a spatial resolution that notably surpasses the light diffraction limit throughout the entire mid-IR spectral range. PTIR nanoscale spectra and images allow the identification of compositionally and optically similar yet distinct materials; organic, inorganic, and composite samples can be studied with this nanoscale analog of infrared spectroscopy, suggesting broad applicability. Additionally, we compare the results obtained with the two tunable lasers, which have different pulse lengths, to experimentally assess the recently developed theory of PTIR signal generation.

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

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.

Nanoscale Infrared Absorption Spectroscopy of Individual Nanoparticles Enabled by Scattering-Type Near-Field Microscopy

Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption.

Nanoscale Infrared Spectroscopy, Technique and Applications

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.