Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 μs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.

Oxygen K-edge and Fe L_2,3-edge electron energy-loss near-edge structures (ELNES) were measured for FeO₆ octahedra and FeO₄ tetrahedra in the brownmillerite Ca(Sr)FeO_2.5 by focusing an electron probe at individual Fe sites using scanning transmission electron microscopy combined with electron energy-loss spectroscopy. The observed site-resolved oxygen K-ELNES showed different features reflecting the local chemical bonding around the FeO₆ octahedra and FeO₄ tetrahedra. A pre-peak in the O K-edge spectra, which is attributed to a transition to an unoccupied O 2p band hybridized with the Fe-3d band, shows splitting in the spectrum of the FeO₆ octahedral site. Additionally, for the oxygen linking the octahedral and tetrahedral Fe sites in CaFeO_2.5, charge transfer was found to preferentially occur toward the tetrahedral Fe ions. In the case of SrFeO_2.5, charge transfer from the oxygen located in the ac plane was biased toward the tetrahedral Fe atoms. Based upon an analysis of the pre-peak intensity of the O K-ELNES, it was concluded that bonding between the oxygen and iron atoms at the tetrahedral site was more covalent in character than at the octahedral site. The strong covalent character of the tetrahedral sites would be one of the reasons for distortion in the FeO₆ octahedra in Ca(Sr)FeO_2.5, as exhibited by an extension along the b-axis.

The structural analysis of crystal defects in organic thin films provides fundamental insights into their electronic properties for applications such as field effect transistors. Observation of crystal defects in organic thin films has previously been performed at rather low resolution by conventional transmission electron microscopy based on phase-contrast imaging. Herein, we apply for the first time annular dark-field imaging to the direct observation of grain boundaries in copper hexachlorophthalocyanine thin films at the atomic resolution level by using an aberration-corrected scanning transmission electron microscope combined with electron energy-loss spectroscopy. By using a low-dose technique and an optimized detection angle, we were able to visualize the contrast of light element (C and N) together with the heavier elements (Cl and Cu) within the molecular column. We were also able to identify unexpected molecular orientations in the grain boundaries along the {110} crystallographic planes giving rise to stacking faults.