Abstract

In this Review, an emerging research field of near-field fluorescence and photochemistry studies on molecular materials is introduced and relevant background, instrumentation, attractive topics, and future perspectives are discussed. Principles of near-field scanning optical microscope and technically important points are described, and our picosecond near-field fluorescence microspectroscopic system is explained. Its high performance of 100 nm spatial, a few ps temporal, and 1 nm spectral resolutions makes it possible to correlate topography, fluorescence image, fluorescence spectrum, and fluorescence rise and decay curve with each other. Near-field fluorescence spectroscopy reveals thickness-dependent fluorescence spectra of tetracene microcrystals, relations between photophysics and morphology of charge transfer microcrystals, and inhomogeneous inner structure of single microcrystals in anthracene-tetracene films. Similar fluorescence and morphology studies are described for polymer films, Langmuir-Blodgett films, and J aggregates. Some anthracene solids show interesting photothermal and photochemical nanometer morphological changes, while photoisomerization in organic crystals, and photolithography and ablation of polymer films upon near-field excitation are introduced. Future perspectives near-field excitation with shorter wavelength and/or higher intensity and various kinds of pump-probe measurement are discussed in view of photochemistry studies.

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