Revealing the three-dimensional arrangement of polar topology in nanoparticles.

In the early 2000s, low dimensional ferroelectric systems were predicted to have topologically nontrivial polar structures, such as vortices or skyrmions, depending on mechanical or electrical boundary conditions. A few variants of these structures have been experimentally observed in thin film model systems, where they are engineered by balancing electrostatic charge and elastic distortion energies. However, the measurement and classification of topological textures for general ferroelectric nanostructures have remained elusive, as it requires mapping the local polarization at the atomic scale in three dimensions. Here we unveil topological polar structures in ferroelectric BaTiO3 nanoparticles via atomic electron tomography, which enables us to reconstruct the full three-dimensional arrangement of cation atoms at an individual atom level. Our three-dimensional polarization maps reveal clear topological orderings, along with evidence of size-dependent topological transitions from a single vortex structure to multiple vortices, consistent with theoretical predictions. The discovery of the predicted topological polar ordering in nanoscale ferroelectrics, independent of epitaxial strain, widens the research perspective and offers potential for practical applications utilizing contact-free switchable toroidal moments.

Hydrophilic Photocrosslinkers as a Universal Solution to Endow Water Affinity to a Polymer Photocatalyst for an Enhanced Hydrogen Evolution Rate.

A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL-R) or ethylene glycol-based bridge chains (CL-TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL-TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5-fold compared to that obtained using non-crosslinked F8BT photocatalysts, whereas CL-R-based photocatalysts yield HER rates comparable to those of non-crosslinked counterparts. Photophysical analyses including time-resolved photoluminescence and transient absorption measurements reveal that adding CL-TEG accelerates exciton separation, forming long-lived charge carriers. Additionally, the in-depth study using molecular dynamics simulations elucidates the dual role of CL-TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high-permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.

Photophore-Anchored Molecular Switch for High-Performance Nonvolatile Organic Memory Transistor.

Over the past decade, molecular-switch-embedded memory devices, particularly field-effect transistors (FETs), have gained significant interest. Molecular switches are integrated to regulate the resistance or current levels in FETs. Despite substantial efforts, realizing large memory window with a long retention time, a critical factor in memory device functionality, remains a challenge. This is due to the inability of an isomeric state of a molecular switch to serve as a stable deep trap state within the semiconductor layer. Herein, the study addresses this limitation by introducing chemical bonding between molecular switch and conjugated polymeric semiconductor, facilitating closed isomer of diarylethene (DAE) to operate as a morphologically stable deep trap state. Azide- and diazirine-anchored DAEs are synthesized, which form chemical bonds to the polymer through photocrosslinking, thereby implementing permanent and controllable trapping states nearby conjugated backbone of polymer semiconductor. Consequently, when diazirine-anchored DAE is blended with F8T2 and subjected to photocrosslinking, the resulting organic FETs exhibit remarkable memory performance, including a memory window of 22 V with a retention time over 106 s, a high photoprogrammable on/off ratio over 103, and a high operational stability over 100 photocycles. Further, photophore-anchored DAEs can achieve precise patterning, which enables meticulous control over the semiconductor layer structure.