Výsledky projektu Mapování fotonově-fyzikálních jevů na jednotlivých molekulách pomocí rastrovací sondy

Interplay between motion of nuclei and excitations has an important role in molecular photophysics of natural and artificial structures. Here we provide a detailed analysis of coupling between quantized librational modes (librons) and charged excited states (trions) on single phthalocyanine dyes adsorbed on a surface. By means of tip-induced electroluminescence performed with a scanning probe microscope, we identify libronic signatures in spectra of chirally adsorbed phthalocyanines and find that these signatures are absent from spectra of symmetrically adsorbed species. We create a model of the libronic coupling based on the Franck-Condon principle to simulate the spectral features. Experimentally measured librational spectra match very well the theoretically calculated librational eigenenergies and peak intensities (Franck-Condon factors). Moreover, the comparison reveals an unexpected depopulation channel for the zero libron of the excited state that can be effectively controlled by tuning the size of the nanocavity. Our results showcase the possibility of characterizing the dynamics of molecules by their low-energy molecular modes using µeV-resolved tip-enhanced spectroscopy.

DOI: 10.1063/5.0048476
Constant amplitude bias modulation over a broad range of microwave frequencies is a prerequisite for application in high-resolution spectroscopic techniques in a tunnel junction, e.g., electron spin resonance spectroscopy or optically detected paramagnetic resonance. Here, we present an optical method for determining the frequency-dependent magnitude of the transfer function of a dedicated high-frequency line integrated with a scanning probe microscope. The method relies on determining the energy cutoff of the plasmonic electroluminescence spectrum, which is linked to the energies of the electrons inelastically tunneling across the junction. We develop an easy-to-implement procedure for effective compensation of an radio frequency line and determination of the transfer function magnitude in the GHz range. We compare our method with conventional fully electronic calibration and find a perfect agreement.

DOI: 10.1021/acsnano.1c01318
Charged optical excitations (trions) generated by charge carrier injection are crucial for emerging optoelectronic technologies as they can be produced and manipulated by electric fields. Trions and neutral excitons can be efficiently induced in single molecules by means of tip-enhanced spectromicroscopic techniques. However, little is known of the exciton-trion dynamics at single molecule level as this requires methods permitting simultaneous subnanometer and subnanosecond characterization. Here, we investigate exciton-trion dynamics by phase fluorometry, combining radio frequency modulated scanning tunnelling luminescence with time-resolved single photon detection. We generate excitons and trions in single Zinc Phthalocyanine (ZnPc) molecules on NaCl/Ag(111), and trace the evolution of the system in the picosecond range. We explore the dependence of effective lifetimes on bias voltage and describe the conversion mechanism from neutral excitons to trions, via charge capture, as the primary pathway to trion formation. We corroborate the dynamics of the system by a causally deterministic four-state model.

With this paper, the primary objective was fulfilled. We show that the adsorption position (Na vs. Cl in the NaCl lattice and number of NaCl layers 2 vs. 3) of the CuPc molecules influences the exciton energy. With the help of TD-DFT calculations we explained this effect by spatially dependent Coulomb interaction occurring at the molecule–insulator interface, which tunes the local dielectric environment of the emitter.

DOI: 10.1021/acsnano.1c08816
Entanglement of excitons holds great promise for the future of quantum computing, which would use individual molecular dyes as building blocks of their circuitry. Studying entangled excitonic eigenstates emerging in coupled molecular assemblies in the near-field with submolecular resolution has the potential to bring insight into the photophysics of these fascinating quantum phenomena. In contrast to far-field spectroscopies, near-field spectroscopic mapping permits direct identification of the individual eigenmodes, type of exciton coupling, including excited states otherwise inaccessible in the far field (dark states). Here we combine tip-enhanced spectromicroscopy with atomic force microscopy to inspect delocalized single-exciton states of charged molecular assemblies engineered from individual perylenetetracarboxylic dianhydride (PTCDA) molecules. Hyperspectral mapping of the eigenstates and comparison with calculated many-body optical transitions reveals a second low-lying excited state of the anion monomers and its role in the exciton entanglement within the assemblies. We demonstrate control over the exciton coupling by switching the assembly charge states. Our results reveal the possibility of tailoring excitonic properties of organic dye aggregates for advanced functionalities and establish the methodology to address them individually at the nanoscale.