Spektroskopie individuálních molekul v nanokavitě rastrovacího tunelového mikroskopu

Doležal, Jiří

Scanning tunneling microscopy-induced luminescence (STML) combined with high- resolution atomic force microscopy (AFM) is a powerful tool for studying the photophysics of individual molecular emitters on surfaces. However, the mechanism of energy conver- sion between tunneling electrons and photons in decoupled systems placed in a nanocavity of STM is not fully understood as it depends on many variables. This thesis presents a range of proof-of-concept experimental approaches. The vi- ability of CO-terminated tips for STML is demonstrated by performing subnanometer- resolved spectroscopy and mapping of photon intensity acquired over zinc phthalocyanine on NaCl/metal substrate. For the same molecule, time-resolved phase fluorometry is de- vised and is used to reveal the exciton and charge dynamics as a function of the applied bias voltage. Of more fundamental character, the role of the chromophore environment on its exciton emission and binding energy is studied. For the first time, we observed and explained the presence of molecular librations in molecules on the surface from a comb-like emission line resulting from the exciton-libron coupling and the chiral adsorp- tion geometry. Finally, exciton delocalization in molecular aggregates is mapped using the tip nanocavity capable of detecting the dark states,...

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