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.

Shortwave Infrared Organic Photodiodes Realized by Polaron Engineering.

A novel approach for developing shortwave IR (SWIR) organic photodiodes (OPDs) using doped polymers is presented. SWIR OPDs are challenging to produce because of the limitations in extending the absorption of conjugated molecules and the high dark currents of SWIR-absorbing materials. Herein, it is shown that the conversion of bound polarons to free polarons by light energy can be utilized as an SWIR photodetection mechanism. To maximize the bound-polaron density and bound-to-free polaron ratio of the doped polymer film, the doping process is engineered and dopant molecules are diffused into the crystalline domain of the polymer matrix and a direct correlation between the bound-to-free polaron ratio and device performance is confirmed. The optimized double-doped SWIR OPD exhibits a high external quantum efficiency of 77 100% and specific detectivity of 1.11 × 1011 Jones against SWIR. These findings demonstrate the application potential of polarons as alternatives for Frenkel excitons in SWIR OPDs.

Liquid-Film Rupture for Web-like Ag Nanowires toward High-Performance Organic Schottky Barrier Transistors.

Organic vertical transistors are promising device with benefits such as high operation speed, high saturation current density, and low-voltage operation owing to their short channel length. However, a short channel length leads to a high off-current, which is undesirable because it affects the on-off ratio and power consumption. This study presents a breakthrough in the development of high-performance organic Schottky barrier transistors (OSBTs) with a low off-current by utilizing a near-ideal source electrode with a web-like Ag nanowire (AgNW) morphology. This is achieved by employing a humidity- and surface-tension-mediated liquid-film rupture technique, which facilitates the formation of well-connected AgNW networks with large pores between them. Therefore, the gate electric field is effectively transmitted to the semiconductor layer. Also, the minimized surface area of the AgNWs causes complete suppression of the off-current and induces ideal saturation of the OSBT output characteristics. p- and n-type OSBTs exhibit off-currents in the picoampere range with on/off ratios exceeding 106 and 105, respectively. Furthermore, complementary inverters are prepared using an aryl azide cross-linker for patterning, with a gain of >16. This study represents a significant milestone in the development of high-performance organic vertical transistors and verifies their applicability in organic electronic circuitry.

Synergistic Contribution of Oligo(ethylene glycol) and Fluorine Substitution of Conjugated Polymer Photocatalysts toward Solar Driven Sacrificial Hydrogen Evolution.

To separately explore the importance of hydrophilicity and backbone planarity of polymer photocatalyst, a series of benzothiadiazole-based donor-acceptor alternating copolymers incorporating alkoxy, linear oligo(ethylene glycol) (OEG) side chain, and backbone fluorine substituents is presented. The OEG side chains in the polymer backbone increase the surface energy of the polymer nanoparticles, thereby improving the interaction with water and facilitating electron transfer to water. Moreover, the OEG-attached copolymers exhibit enhanced intermolecular packing compared to polymers with alkoxy side chains, which is possibly attributed to the self-assembly properties of the side chains. Fluorine substituents on the polymer backbone produce highly ordered lamellar stacks with distinct π-π stacking features; subsequently, the long-lived polarons toward hydrogen evolution are observed by transient absorption spectroscopy. In addition, a new nanoparticle synthesis strategy using a methanol/water mixed solvent is first adopted, thereby avoiding the screening effect of surfactants between the nanoparticles and water. Finally, hydrogen evolution rate of 26 000 µmol g-1  h-1 is obtained for the copolymer incorporated with both OEG side chains and fluorine substituents under visible-light irradiation (λ > 420 nm). This study demonstrates how the glycol side chain strategy can be further optimized for polymer photocatalysts by controlling the backbone planarity.

Azide-functionalized ligand enabling organic-inorganic hybrid dielectric for high-performance solution-processed oxide transistors.

We propose a highly efficient crosslinking strategy for organic-inorganic hybrid dielectric layers using azide-functionalized acetylacetonate, which covalently connect inorganic particles to polymers, enabling highly efficient inter- and intra-crosslinking of organic and inorganic inclusions, resulting in a dense and defect-free thin-film morphology. From the optimized processing conditions, we obtained an excellent dielectric strength of over 4.0 MV cm-1, a high dielectric constant of ~14, and a low surface energy of 38 mN m-1. We demonstrated the fabrication of exceptionally high-performance, hysteresis-free n-type solution-processed oxide transistors comprising an In2O3/ZnO double layer as an active channel with an electron mobility of over 50 cm2 V-1 s-1, on/off ratio of ~107, subthreshold swing of 108 mV dec-1, and high bias-stress stability. From temperature-dependent I-V analyses combined with charge transport mechanism analyses, we demonstrated that the proposed hybrid dielectric layer provides percolation-limited charge transport for the In2O3/ZnO double layer under field-effect conditions.

Direct strain correlations at the single-atom level in three-dimensional core-shell interface structures.

Nanomaterials with core-shell architectures are prominent examples of strain-engineered materials. The lattice mismatch between the core and shell materials can cause strong interface strain, which affects the surface structures. Therefore, surface functional properties such as catalytic activities can be designed by fine-tuning the misfit strain at the interface. To precisely control the core-shell effect, it is essential to understand how the surface and interface strains are related at the atomic scale. Here, we elucidate the surface-interface strain relations by determining the full 3D atomic structure of Pd@Pt core-shell nanoparticles at the single-atom level via atomic electron tomography. Full 3D displacement fields and strain profiles of core-shell nanoparticles were obtained, which revealed a direct correlation between the surface and interface strain. The strain distributions show a strong shape-dependent anisotropy, whose nature was further corroborated by molecular statics simulations. From the observed surface strains, the surface oxygen reduction reaction activities were predicted. These findings give a deep understanding of structure-property relationships in strain-engineerable core-shell systems, which can lead to direct control over the resulting catalytic properties.

Comparative study of PMS oxidation with Fenton oxidation as an advanced oxidation process for Co-EDTA decomplexation.

In nuclear industry, Co-EDTA complex is generated due to the decontamination activities of nuclear power plants (NPPs). This complex is extremely refractory to the convention methods and can escalate the mobility of Co radionuclide in the environment. Due to its hazardous impact on human and environment, the effective treatments of Co-EDTA complexes are highly recommended. In this study, for the first time, we applied both hydroxyl (OH) and sulfate radical (SO4-) based advanced oxidation processes (AOPs) namely Fenton and peroxymonosulfate (PMS) reactions for the Co-EDTA decomplexation. Both reactions exhibited higher Co-EDTA decomplexation at pH = 3, however, the PMS based reaction was found to be superior, which showed highest decomplexation efficiency (without pH adjustment) over Fenton reaction (pH = 1-13). Moreover, PMS based system was found to be more suitable than Fenton reaction, because PMS showed best Co-EDTA decomplexation efficiency without any additional catalyst dosages at the shorter reaction time. XRD data confirmed the presence of both CoO and Co(OH)2 in the precipitates after treatment. The electron spin resonance spectroscopy (ESR) analysis identified OH and SO4- in Fenton and PMS system, respectively. From this study, we believe that PMS based reaction is a superior alternative of Fenton reaction for the Co-EDTA decomplexation.

Direct Observation of Three-Dimensional Atomic Structure of Twinned Metallic Nanoparticles and Their Catalytic Properties.

We determined a full 3D atomic structure of a dumbbell-shaped Pt nanoparticle formed by a coalescence of two nanoclusters using deep learning assisted atomic electron tomography. Formation of a double twin boundary was clearly observed at the interface, while substantial anisotropy and disorder were also found throughout the nanodumbbell. This suggests that the diffusion of interfacial atoms mainly governed the coalescence process, but other dynamic processes such as surface restructuring and plastic deformation were also involved. A full 3D strain tensor was clearly mapped, which allows direct calculation of the oxygen reduction reaction activity at the surface. Strong tensile strain was found at the protruded region of the nanodumbbell, which results in an improved catalytic activity on {100} facets. This work provides important clues regarding the coalescence mechanism and the relation between the atomic structure and catalytic property at the single-atom level.

Co2+/PMS based sulfate-radical treatment for effective mineralization of spent ion exchange resin.

Sulfate radical advance oxidation processes (SR-AOPs) have attracted a greater attention as a suitable alternative of the hydroxyl radical based advance oxidation process (HR-AOPs). In this study, for the first time we report liquid phase mineralization of nuclear grade cationic IRN-77 resin in Co2+/peroxymonosulfate (PMS) based SR-AOPs. After the dissolution of cationic IRN-77 resin, 30 volatile and 15 semi-volatile organic compounds were analyzed/detected using non-targeted GC-MS analysis. The optimal reaction parameters for the highest chemical oxygen demand (COD) removal (%) of IRN-77 resin were determined, and the initial pH, PMS dosage, and reaction temperature were found to be the most influential parameters for the resin degradation. We successfully achieved ∼90% COD removal (1000 mg/L; 1000 ppm) of dissolved spent resin for SR-AOPs by optimizing the reaction parameters as initial pH = 9, Co2+ = 4 mM (catalyst), PMS = 60 mM (as oxidant) at 60 °C temperature for 60 min reaction. The electron spin resonance spectroscopy (ESR) spectra confirmed the presence of SO4∙- and OH∙ as main reactive species in the Co2+/PMS resin system. In addition, Fourier transform infrared spectroscopy (FT-IR) analyses were used for structural characterization of solid and liquid phase resin samples. We believe that this work will offer a robust approach for the effective treatment of spent resin generated from nuclear industry.

Sublimation-doping with super bases for high-performance solution-processed heterojunction oxide thin film transistors.

We elucidate how non-destructive sublimation-doping of In2O3/ZnO heterojunctions with various amidine-based organic dopants affects the degree of band bending of the heterojunction and thus the overall performance of solution-processed heterojunction oxide thin-film transistors (TFTs). Ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy analyses show that the stronger the basicity of the dopant, the smaller the EC - EF of ZnO that can be induced within a short doping time, resulting in a high electron mobility due to the increased electron density of the In2O3 layer at the vicinity of the heterointerface. Mott-Schottky analysis combined with secondary ion mass spectroscopy shows the preferential modification of EC - EF selectively for the ZnO layer. The use of a super base with the highest basicity exhibits a high electron mobility of 17.8 cm2 V-1 s-1 for the SiO2 and 37.8 cm2 V-1 s-1 on average (46.6 cm2 V-1 s-1 maximum) for the ZrO2 dielectric layers and enhanced operational bias-stress stability via sublimation-doping for 6 min, which can be attributed to the trap-filled, percolation-limited charge transport behavior. Reproducibility tests are conducted for more than 50 independently fabricated TFTs using the optimized doping technique, and electron mobility distributions with deviations <±10% are demonstrated. This study shows that sublimation doping with super bases can be a good solution for high mobility oxide TFTs with stability and reliability.

Development of geopolymer waste form for immobilization of radioactive borate waste.

Radioactive borate waste containing a high concentration of boron (B) is problematic to be solidified using cement because soluble borate such as boric acid hinders the hydration reaction. In this study, borate waste was used as a raw material for metakaolin-based geopolymer according to the characteristic that B replaces a part of Si. Geopolymers using KOH alkaline activator (K-geopolymers) showed higher compressive strength than geopolymers using NaOH alkaline activator (Na-geopolymer). In addition, the compressive strength increased proportionally to the Si/(Al+B) ratio regardless of the alkaline cation species. These variations in compressive strength might be due to the viscosity of the geopolymer mixture, atomic size of alkaline cations, and the increase in Si content. The characteristic analyses (XRD, FT-IR, and solid state 11B MAS NMR) indicated that B was incorporated into the geopolymer structure. Thus, the K-geopolymer has a dense and homogeneous microstructure. In a semi-dynamic leaching test, less B leached from the geopolymers compared to the cement waste form. Consequently, borate waste can be solidified using metakaolin-based geopolymer, and the use of a KOH alkaline activator is advantageous in terms of mechanical property and structural durability.

Single-atom level determination of 3-dimensional surface atomic structure via neural network-assisted atomic electron tomography.

Functional properties of nanomaterials strongly depend on their surface atomic structures, but they often become largely different from their bulk structures, exhibiting surface reconstructions and relaxations. However, most of the surface characterization methods are either limited to 2D measurements or not reaching to true 3D atomic-scale resolution, and single-atom level determination of the 3D surface atomic structure for general 3D nanomaterials still remains elusive. Here we demonstrate the measurement of 3D atomic structure at 15 pm precision using a Pt nanoparticle as a model system. Aided by a deep learning-based missing data retrieval combined with atomic electron tomography, the surface atomic structure was reliably measured. We found that <[Formula: see text]> and <[Formula: see text]> facets contribute differently to the surface strain, resulting in anisotropic strain distribution as well as compressive support boundary effect. The capability of single-atom level surface characterization will not only deepen our understanding of the functional properties of nanomaterials but also open a new door for fine tailoring of their performance.