ABSTRACT
Given its central role in utilizing light energy, photoinduced electron transfer (PET) from an excited molecule has been widely studied1-6. However, even though microscopic photocurrent measurement methods7-11 have made it possible to correlate the efficiency of the process with local features, spatial resolution has been insufficient to resolve it at the molecular level. Recent work has, however, shown that single molecules can be efficiently excited and probed when combining a scanning tunnelling microscope (STM) with localized plasmon fields driven by a tunable laser12,13. Here we use that approach to directly visualize with atomic-scale resolution the photocurrent channels through the molecular orbitals of a single free-base phthalocyanine (FBPc) molecule, by detecting electrons from its first excited state tunnelling through the STM tip. We find that the direction and the spatial distribution of the photocurrent depend sensitively on the bias voltage, and detect counter-flowing photocurrent channels even at a voltage where the averaged photocurrent is near zero. Moreover, we see evidence of competition between PET and photoluminescence12, and find that we can control whether the excited molecule primarily relaxes through PET or photoluminescence by positioning the STM tip with three-dimensional, atomic precision. These observations suggest that specific photocurrent channels can be promoted or suppressed by tuning the coupling to excited-state molecular orbitals, and thus provide new perspectives for improving energy-conversion efficiencies by atomic-scale electronic and geometric engineering of molecular interfaces.
ABSTRACT
Because the spatial distribution of frontier molecular orbitals (FMOs) regulates the thermally activated delayed fluorescence (TADF) property, researchers synthesize TADF emitters by designing their FMO distribution. However, it remains challenging to clarify how the FMO distribution is altered at molecular interfaces. Thus, visualizing the FMOs at molecular interfaces helps us to understand the working behavior of TADF emitters. Using scanning tunneling microscopy (STM), we investigated the electronic structure of a single TADF emitter, hexamethylazatriangulene-triazine, at molecule-metal and molecule-insulating film interfaces. FMOs at the molecule-metal interface were not spatially confined to the donor-acceptor moieties because of hybridization. Meanwhile, FMOs at the molecule-insulator interface exhibited spatially separated filled and empty states confined to each moiety, similar to the calculated gas-phase FMOs. These observations illustrate that the molecule-environment interaction alters the spatial distribution of FMOs, proving that STM is a powerful tool for studying TADF molecules.
ABSTRACT
A wideband cryogenic amplifier has been developed for low temperature scanning tunneling microscopy. The amplifier consisting of a wideband complementary metal oxide semiconductor field effect transistors operational amplifier together with a feedback resistor of 100 kΩ and a capacitor is mounted within a 4 K Dewar. This amplifier has a wide bandwidth and is successfully applied to scanning tunneling microscopy applications at low temperatures down to â¼7 K. The quality of the designed amplifier is validated by high resolution imaging. More importantly, the amplifier has also proved to be capable of performing scanning tunneling spectroscopy measurements, showing the detection of the Shockley surface state of the Au(111) surface and the superconducting gap of Nb(110).
ABSTRACT
We report a serendipitous discovery of light-induced generation of a circular microstructure on a glass surface. The microstructure has a ring shape with notable photophysical properties such as highly bright luminescence and strong resistance to photobleaching. We investigated the formation process as well as the luminescence properties of the micro ring to understand the origin of this peculiar phenomenon.
