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The rich physical properties unveiled in a plethora of transition and rare-earth metal oxides have been attributed to the intricate interplays between the orbital, charge, and spin degrees of freedom. Among them, rare-earth manganites (RMnO3) have been attracting tremendous attention owing to the ionic size-induced lattice distortion dictated by the Goldschmidt tolerance factor and the substantial Jahn–Teller distortion unique to Mn3+ ions, which evidently have resulted in a variety of emergent characteristics in electronic, magnetic, and orbital ordering. In this work, we deliberately engineered the orientation of a series of orthorhombic YMnO3 (o-YMO) films grown on SrTiO3(100) [STO(100)] and SrTiO3(110) [STO(110)] substrates by means of pulsed laser deposition. The x-ray diffraction (XRD) and reciprocal space mapping revealed that o-YMO/STO(100) is c-axis-oriented and o-YMO/STO(110) is a-axis-oriented, respectively. The XRD ϕ-scans further indicate that both films have excellent in-plane crystallinity, allowing the exploration of anisotropies along the respective crystallographic orientations. Indeed, the x-ray absorption linear dichroism spectroscopy taken along the respective crystallographic orientations evidently exhibited substantial anisotropy. Theoretical fitting with configuration interaction cluster calculations suggests that the d 3 z 2 − r 2 orbitals are parallel to YMO[001]/(100), leading to stronger electron scattering along the c-axis. Independent polarization-dependent Δ R/R spectra obtained using the femtosecond pump–probe method exhibited substantial anisotropic behaviors in carrier relaxation dynamics when probing along different crystallographic orientations, presumably due to orbital ordering anisotropies. [ABSTRACT FROM AUTHOR]

Self-assembled vertical heterostructure with a high interface-to-volume ratio offers tremendous opportunities to realize intriguing properties and advanced modulation of functionalities. Here, a heterostructure composed of two visible-light photocatalysts, BiFeO3 (BFO) and ε-Fe2O3 ( ε-FO), is designed to investigate its photoelectrochemical performance. The structural characterization of the BFO-FO heterostructures confirms the phase separation with BFO nanopillars embedded in the ε-FO matrix. The investigation of band structure of the heterojunction suggests the assistance of photoexcited carrier separation, leading to an enhanced photoelectrochemical performance. The insights into the charge separation are further revealed by means of ultrafast dynamics and electrochemical impedance spectroscopies. This work shows a delicate design of the self-assembled vertical heteroepitaxy by taking advantage of the intimate contact between two phases that can lead to a tunable charge interaction, providing a new configuration for the optimization of photoelectrochemical cell. [ABSTRACT FROM AUTHOR]

In the pursuit of novel functionalities by utilizing the lattice degree of freedom in complex oxide heterostructure, the control mechanism through direct strain manipulation across the interfaces is still under development, especially with various stimuli, such as electric field, magnetic field, light, etc. In this study, the superlattices consisting of colossal-magnetoresistive manganites La0.7Sr0.3MnO3 (LSMO) and photostrictive SrRuO3 (SRO) have been designed to investigate the light-dependent controllability of lattice order in the corresponding functionalities and rich interface physics. Two substrates, SrTiO3 (STO) and LaAlO3 (LAO), have been employed to provide the different strain environments to the superlattice system, in which the LSMO sublayers exhibit different orbital occupations. Subsequently, by introducing light, we can modulate the strain state and orbital preference of LSMO sublayers through light-induced expansion of SRO sublayers, leading to surprisingly opposite changes in photoresistivity. The observed photoresistivity decreases in the superlattice grown on STO substrate while increases in the superlattice grown on LAO substrate under light illumination. This work has presented a model system that demonstrates the manipulation of orbital-lattice coupling and the resultant functionalities in artificial oxide superlattices via light stimulus. [ABSTRACT FROM AUTHOR]

The energy transfer (ET) between organic molecules and semiconductors is a crucial mechanism for enhancing the performance of semiconductor-based optoelectronic devices, but it remains undiscovered. Here, ultrafast optical pump-probe spectroscopy was utilized to directly reveal the ET between organic Alq 3 molecules and Si semiconductors. Ultrathin SiO 2 dielectric layers with a thickness of 3.2-10.8 nm were inserted between Alq 3 and Si to prevent charge transfer. By means of the ET from Alq 3 to Si, the SiO 2 thickness-dependent relaxation dynamics of photoexcited carriers in Si have been unambiguously observed on the transient reflectivity change (Δ R / R ) spectra, especially for the relaxation process on a time scale of 200-350 ps. In addition, these findings also agree with the results of our calculation in a model of long-range dipole-dipole interactions, which provides critical information for developing future optoelectronic devices.

"Spin" has been recently reported as an important degree of electronic freedom to improve the performance of electrocatalysts and photocatalysts. This work demonstrates the manipulations of spin-polarized electrons in CsPbBr 3 halide perovskite nanoplates (NPLs) to boost the photocatalytic CO 2 reduction reaction (CO 2 RR) efficiencies by doping manganese cations (Mn 2+ ) and applying an external magnetic field. Mn-doped CsPbBr 3 (Mn-CsPbBr 3 ) NPLs exhibit an outstanding photocatalytic CO 2 RR compared to pristine CsPbBr 3 NPLs due to creating spin-polarized electrons after Mn doping. Notably, the photocatalytic CO 2 RR of Mn-CsPbBr 3 NPLs is significantly enhanced by applying an external magnetic field. Mn-CsPbBr 3 NPLs exhibit 5.7 times improved performance of photocatalytic CO 2 RR under a magnetic field of 300 mT with a permanent magnet compared to pristine CsPbBr 3 NPLs. The corresponding mechanism is systematically investigated by magnetic circular dichroism spectroscopy, ultrafast transient absorption spectroscopy, and density functional theory simulation. The origin of enhanced photocatalytic CO 2 RR efficiencies of Mn-CsPbBr 3 NPLs is due to the increased number of spin-polarized photoexcited carriers by synergistic doping of the magnetic elements and applying a magnetic field, resulting in prolonged carrier lifetime and suppressed charge recombination. Our result shows that manipulating spin-polarized electrons in photocatalytic semiconductors provides an effective strategy to boost photocatalytic CO 2 RR efficiencies.

The adsorption and desorption of electrolyte ions strongly modulates the carrier density or carrier type on the surface of monolayer-MoS 2 catalyst during the hydrogen evolution reaction (HER). The buildup of electrolyte ions onto the surface of monolayer MoS 2 during the HER may also result in the formation of excitons and trions, similar to those observed in gate-controlled field-effect transistor devices. Using the distinct carrier relaxation dynamics of excitons and trions of monolayer MoS 2 as sensitive descriptors, an in situ microcell-based scanning time-resolved liquid cell microscope is set up to simultaneously measure the bias-dependent exciton/trion dynamics and spatially map the catalytic activity of monolayer MoS 2 during the HER. This operando probing technique used to monitor the interplay between exciton/trion dynamics and electrocatalytic activity for two-dimensional transition metal dichalcogenides provides an excellent platform to investigate the local carrier behaviors at the atomic layer/liquid electrolyte interfaces during electrocatalytic reaction.

Multiferroics-materials that exhibit coupled ferroic orders-are considered to be one of the most promising candidate material systems for next-generation spintronics, memory, low-power nanoelectronics and so on. To advance potential applications, approaches that lead to persistent and extremely fast functional property changes are in demand. Herein, it is revealed that the phase transition and the correlated ferroic orders in multiferroic BiFeO 3 (BFO) can be modulated via illumination of single short/ultrashort light pulses. Heat transport simulations and ultrafast optical pump-probe spectroscopy reveal that the transient strain induced by light pulses plays a key role in determining the persistent final states. Having identified the diffusionless phase transformation features via scanning transmission electron microscopy, sequential laser pulse illumination is further demonstrated to perform large-area phase and domain manipulation in a deterministic way. The work contributes to all-optical and rapid nonvolatile control of multiferroicity, offering different routes while designing novel optoelectronics., (© 2020 Wiley-VCH GmbH.)