Interface Control of Ferroelectricity in an SrRuO3/BaTiO3/SrRuO3 Capacitor and its Critical Thickness

The atomic‐scale synthesis of artificial oxide heterostructures offers new opportunities to create novel states that do not occur in nature. The main challenge related to synthesizing these structures is obtaining atomically sharp interfaces with designed termination sequences. In this study, it is demonstrated that the oxygen pressure during growth plays an important role in controlling the interfacial terminations of SrRuO₃/BaTiO₃/SrRuO₃ (SRO/BTO/SRO) ferroelectric (FE) capacitors. The SRO/BTO/SRO heterostructures are grown by a pulsed laser deposition method. The top SRO/BTO interface, grown at high (around 150 mTorr), usually exhibits a mixture of RuO₂–BaO and SrO–TiO₂ terminations. By reducing , the authors obtain atomically sharp SRO/BTO top interfaces with uniform SrO–TiO₂ termination. Using capacitor devices with symmetric and uniform interfacial termination, it is demonstrated for the first time that the FE critical thickness can reach the theoretical limit of 3.5 unit cells.     

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High‐Ni Layered Oxide Cathodes

Nickel‐rich layered transition metal oxides, LiNi_1?x (MnCo)_x O₂ (1?x ≥ 0.5), are appealing candidates for cathodes in next‐generation lithium‐ion batteries (LIBs) for electric vehicles and other large‐scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi_0.7Mn_0.15Co_0.15O₂ (NMC71515) by solid‐state methods are investigated through a combination of time‐resolved in situ high‐energy X‐ray diffraction and absorption spectroscopy measurements. The real‐time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal‐driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high‐Ni layered oxide cathodes for LIBs.     

Brain‐Inspired Photonic Neuromorphic Devices using Photodynamic Amorphous Oxide Semiconductors and their Persistent Photoconductivity

The combination of a neuromorphic architecture and photonic computing may open up a new era for computational systems owing to the possibility of attaining high bandwidths and the low‐computation‐power requirements. Here, the demonstration of photonic neuromorphic devices based on amorphous oxide semiconductors (AOSs) that mimic major synaptic functions, such as short‐term memory/long‐term memory, spike‐timing‐dependent plasticity, and neural facilitation, is reported. The synaptic functions are successfully emulated using the inherent persistent photoconductivity (PPC) characteristic of AOSs. Systematic analysis of the dynamics of photogenerated carriers for various AOSs is carried out to understand the fundamental mechanisms underlying the photoinduced carrier‐generation and relaxation behaviors, and to search for a proper channel material for photonic neuromorphic devices. It is found that the activation energy for the neutralization of ionized oxygen vacancies has a significant influence on the photocarrier‐generation and time‐variant recovery behaviors of AOSs, affecting the PPC behavior.     

Fabrication of Millimeter‐Long Carbon Tubular Nanostructures Using the Self‐Rolling Process Inherent in Elastic Protein Layers

Millimeter‐long conducting fibers can be fabricated from carbon nanomaterials via a simple method involving the release of a prestrained protein layer. This study shows how a self‐rolling process initiated by polymerization of a micropatterned layer of fibronectin (FN) results in the production of carbon nanomaterial‐based microtubular fibers. The process begins with deposition of carbon nanotube (CNT) or graphene oxide (GO) particles on the FN layer. Before polymerization, particles are discrete and nonconducting, but after polymerization the carbon materials become entangled to form an interconnected conducting network clad by FN. Selective removal of FN using high‐temperature combustion yields freestanding CNT or reduced GO microtubular fibers. The properties of these fibers are characterized using atomic force microscopy and Raman spectroscopy. The data suggest that this method may provide a ready route to rapid design and fabrication of aligned biohybrid nanomaterials potentially useful for future electronic applications.     

Direct Observation of Inherent Atomic‐Scale Defect Disorders responsible for High‐Performance Ti1−xHfxNiSn1−ySby Half‐Heusler Thermoelectric Alloys

Structural defects often dominate the electronic‐ and thermal‐transport properties of thermoelectric (TE) materials and are thus a central ingredient for improving their performance. However, understanding the relationship between TE performance and the disordered atomic defects that are generally inherent in nanostructured alloys remains a challenge. Herein, the use of scanning transmission electron microscopy to visualize atomic defects directly is described and disordered atomic‐scale defects are demonstrated to be responsible for the enhancement of TE performance in nanostructured Ti_1?x Hf_x NiSn_1?y Sb_y half‐Heusler alloys. The disordered defects at all atomic sites induce a local composition fluctuation, effectively scattering phonons and improving the power factor. It is observed that the Ni interstitial and Ti,Hf/Sn antisite defects are collectively formed, leading to significant atomic disorder that causes the additional reduction of lattice thermal conductivity. The Ti_1?x Hf_x NiSn_1?y Sb_y alloys containing inherent atomic‐scale defect disorders are produced in one hour by a newly developed process of temperature‐regulated rapid solidification followed by sintering. The collective atomic‐scale defect disorder improves the zT to 1.09 ± 0.12 at 800 K for the Ti_0.5Hf_0.5NiSn_0.98Sb_0.02 alloy. These results provide a promising avenue for improving the TE performance of state‐of‐the‐art materials.     

Atomic-Scale Metal–Insulator Transition in SrRuO3 Ultrathin Films Triggered by Surface Termination Conversion

The metal–insulator transition (MIT) in transition-metal-oxide is fertile ground for exploring intriguing physics and potential device applications. Here, an atomic-scale MIT triggered by surface termination conversion in SrRuO₃ ultrathin films is reported. Uniform and effective termination engineering at the SrRuO₃(001) surface can be realized via a self-limiting water-leaching process. As the surface termination converts from SrO to RuO₂, a highly insulating and nonferromagnetic phase emerges within the topmost SrRuO₃ monolayer. Such a spatially confined MIT is corroborated by systematic characterizations on electrical transport, magnetism, and scanning tunneling spectroscopy. Density functional theory calculations and X-ray linear dichroism further suggest that the surface termination conversion breaks the local octahedral symmetry of the crystal field. The resultant modulation in 4d orbital occupancy stabilizes a nonferromagnetic insulating surface state. This work introduces a new paradigm to stimulate and tune exotic functionalities of oxide heterostructures with atomic precision.     

Design Principles and Synergistic Effects of Chlorination on a Conjugated Backbone for Efficient Organic Photovoltaics: A Critical Review

The pursuit of low-cost, flexible, and lightweight renewable power resources has led to outstanding advancements in organic solar cells (OSCs). Among the successful design principles developed for synthesizing efficient conjugated electron donor (ED) or acceptor (EA) units for OSCs, chlorination has recently emerged as a reliable approach, despite being neglected over the years. In fact, several recent studies have indicated that chlorination is more potent for large-scale production than the highly studied fluorination in several aspects, such as easy and low-cost synthesis of materials, lowering energy levels, easy tuning of molecular orientation, and morphology, thus realizing impressive power conversion efficiencies in OSCs up to 17%. Herein, an up-to-date summary of the current progress in photovoltaic results realized by incorporating a chlorinated ED or EA into OSCs is presented to recognize the benefits and drawbacks of this interesting substituent in photoactive materials. Furthermore, other aspects of chlorinated materials for application in all-small-molecule, semitransparent, tandem, ternary, single-component, and indoor OSCs are also presented. Consequently, a concise outlook is provided for future design and development of chlorinated ED or EA units, which will facilitate utilization of this approach to achieve the goal of low-cost and large-area OSCs.