Abstract

Tunable quantum cascade lasers (QCLs) have recently been introduced as mid-infrared (mid-IR) sources for spectroscopic ellipsometric and polarimetric setups. QCLs, with their unique properties with respect to coherence and brilliance in either pulsed or continuous-wave operation, are opening up numerous new possibilities for laboratory and industrial applications. In this review, the authors will focus on thin-film characterization techniques like ellipsometric and nanopolarimetric methods and summarize related state-of-the-art techniques in this rapidly developing field. These methods are highly relevant for optical, electronical, and biomedical applications and allow detailed structural analyses regarding band properties, spectra–structure correlations, and material anisotropy. Compared to classical Fourier-transform-IR spectroscopy, thin-film sensitivity can be achieved at high spectral and spatial resolution (<0.5 cm−1, <150 μm). Measurement times are reducible by several orders of magnitude into the millisecond and microsecond range with laser-based polarimetric setups involving modulation or single-shot concepts. Thus, mid-IR ellipsometric and polarimetric hyperspectral imaging can be performed on the time scale of minutes. For mid-IR ellipsometric imaging, thickness and structure information become simultaneously accessible at spatial resolutions of a few 100 μm and possibly even at the micrometer scale by the integration of microscopic concepts. With the atomic force microscopy-infrared spectroscopy based nanopolarimetric approach, anisotropy in the absorption properties can be investigated with lateral resolutions beyond the diffraction limit, reaching a few 10 nm.

Highlights

  • This article reviews polarization dependent mid-infrared spectroscopic methods and several basic characteristics of the measurement concepts using brilliant light sources

  • Examples of recent results in this field related to the IR ellipsometric,1–5 near-field microscopic,6 and nanopolarimetric atomic force microscopy-infrared spectroscopy (AFM-IR)7–14 analysis of organic thin films and anisotropic molecular aggregates are discussed

  • The availability of tunable quantum cascade lasers (QCLs)22–25 significantly broadened the number of IR spectroscopic applications and motivated novel concepts in the research of solid, liquid, or gaseous materials

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Summary

INTRODUCTION

This article reviews polarization dependent mid-infrared (mid-IR) spectroscopic methods and several basic characteristics of the measurement concepts using brilliant light sources. Examples of recent results in this field related to the IR ellipsometric, near-field microscopic, and nanopolarimetric atomic force microscopy-infrared spectroscopy (AFM-IR) analysis of organic thin films and anisotropic molecular aggregates are discussed Brilliant laboratory sources, such as optical parametric oscillators and laser sources, as well as tunable free-electron lasers (FELs) and synchrotron radiation sources, have been very important in pushing the development of modern mid-IR spectroscopy.. Elaborated polarization dependent IR spectroscopic methods, such as IR ellipsometric and IR nanoscopic techniques, are necessary for a reliable determination of band properties, spectra–structure correlations, and macromolecular orientations in thin films, thereby being essential for comprehensive studies of structured or anisotropic surfaces The latter point is of particular importance in technological. Calculations or simulations based on analytical and/or numerical methods are required in order to achieve a comprehensive in-depth interpretation. For instance, measured IR spectra of inorganic and organic thin films can be interpreted within optical simulations involving oscillator models to describe vibrational or electronic absorptions.

METHODIC ASPECTS
Brilliant radiation sources for mid-infrared spectroscopy
SINGLE-SHOT MID-IR LASER ELLIPSOMETRY
MID-IR LASER NANOPOLARIMETRY
SUMMARY AND CONCLUSIONS
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