New Insight into Microstructure Engineering of Ni-Rich Layered Oxide Cathode for High Performance Lithium Ion Batteries

Ni-rich layered LiNi_xCo_yMn_1−x−yO₂ (LNCM) with Ni content over >90% is considered as a promising lithium ion battery (LIB) cathode, attributed by its low cost and high practical capacity. However, Ni-rich LNCM inevitably suffers rapid capacity fading at a high state of charge due to the mechanochemical breakdown; in particular, the microcrack formation has been regarded as one of the main culprits for Ni-rich layered cathode failure. To address these issues, Ni-rich layered cathodes with a textured microstructure are developed by phosphorous and boron doping. Attributed by the textured morphology, both phosphorous- and boron-doped cathodes suppress microcrack formation and show enhanced cycle stability compared to the undoped cathode. However, there exists a meaningful capacity retention difference between the doped cathodes. By adapting the various analysis techniques, it is shown that the boron-doped Ni-rich layered cathode displays better cycle stability not only by its ability to suppress microcracks during cycling but also by its primary particle morphology that is reluctant to oxygen evolution. The present work reveals that not only restraint of particle cracks but also suppression of oxygen release by developing the oxygen stable facets is important for further improvements in state-of-the-art Li ion battery Ni-rich layered cathode materials.     

Enhanced Optical Properties and Stability of CsPbBr3 Nanocrystals Through Nickel Doping

To improve the quantum efficiency and stability of perovskite quantum dots, the structural and optical properties are optimized by varying the concentration of Ni doping in CsPbBr₃ perovskite nanocrystals (PNCs). As Ni doping is gradually added, a blue shift is observed at the photoluminescence (PL) spectra. Ni-doped PNCs exhibit stronger light emission, higher quantum efficiency, and longer lifetimes than undoped PNCs. The doped divalent element acts as a defect in the perovskite structure, reducing the recombination rate of electrons and holes. A stability test is used to assess the susceptibility of the perovskite to light and moisture. For ultra-violet light irradiation, the PL intensity of undoped PNCs decreases by 70%, whereas that of Ni-doped PNCs decreases by 18%. In the water addition experiment, the PL intensity of Ni-doped PNCs is three times that of undoped PNCs. For CsPbBr₃ and Ni:CsPbBr₃ PNCs, a light emitting diode is fabricated by spin-coating. The efficiency of Ni:CsPbBr₃ exceeds that of CsPbBr₃ PNCs, and the results significantly differ based on the ratio. A maximum luminance of 833 cd m^–2 is obtained at optimum efficiency (0.3 cd A^–1). Therefore, Ni-doped PNCs are expected to contribute to future performance improvements in display devices.     

Highly Reliable Charge Trap-Type Organic Non-Volatile Memory Device Using Advanced Band-Engineered Organic-Inorganic Hybrid Dielectric Stacks

With the recent interest in data storage in flexible electronics, highly reliable charge trap-type organic-based non-volatile memory (CT-ONVM) has attracted much attention. CT-ONVM should have a wide memory window, good endurance, and long-term retention characteristics, as well as mechanical flexibility. This paper proposed CT-ONVM devices consisting of band-engineered organic–inorganic hybrid films synthesized via an initiated chemical vapor deposition process. The synthesized poly(1,3,5-trimethyl-1,3,5,-trivinyl cyclotrisiloxane) and Al hybrid films are used as a tunneling dielectric layer and a blocking dielectric layer, respectively. For the charge trapping layer, different Hf, Zr, and Ti hybrids are examined, and their memory performances are systematically compared. The best combination of hybrid dielectric stacks showed a wide memory window of 6.77 V, good endurance of up to 10⁴ cycles, and charge retention of up to 71% after 10⁸ s even under the 2% strained condition. The CT-ONVM device using the hybrid dielectric stacks outperforms other organic-based charge trap memory devices and is even comparable in performance to conventional inorganic-based poly-silicon/oxide/nitride/oxide/silicon structures devices. The CT-ONVM using hybrid dielectrics can overcome the inherent low reliability and process complexity limitations of organic electronics and expedite the realization of wearable organic electronics.     

Immunoregulation of Macrophages by Controlling Winding and Unwinding of Nanohelical Ligands

Developing materials with the capability of changing their innate features can help to unravel direct interactions between cells and ligand-displaying features. This study demonstrates the grafting of magnetic nanohelices displaying cell-adhesive Arg-Gly-Asp (RGD) ligand partly to a material surface. These enable nanoscale control of rapid winding (“W”) and unwinding (“UW”) of their nongrafted portion, such as directional changes in nanohelix unwinding (lower, middle, and upper directions) by changing the position of a permanent magnet while keeping the ligand-conjugated nanohelix surface area constant. The unwinding (“UW”) setting cytocompatibility facilitates direct integrin recruitment onto the ligand-conjugated nanohelix to mediate the development of paxillin adhesion assemblies of macrophages that stimulate M2 polarization using glass and silicon substrates for in vitro and in vivo settings, respectively, at a single cell level. Real time and in vivo imaging are demonstrated that nanohelices exhibit reversible unwinding, winding, and unwinding settings, which modulate time-resolved adhesion and polarization of macrophages. It is envisaged that this remote, reversible, and cytocompatible control can help to elucidate molecular-level cell–material interactions that modulate regenerative/anti-inflammatory immune responses to implants.     

ZnO Nanoplatelets with Controlled Thickness: Atomic Insight into Facet-Specific Bimodal Ligand Binding Using DNP NMR

Colloidal nanoplatelets (NPLs) and nanosheets with controlled thickness have recently emerged as an exciting new class of quantum-sized nanomaterials with substantially distinct optical properties compared to 0D quantum dots. Zn-based NPLs are an attractive heavy-metal-free alternative to the so far most widespread cadmium chalcogenide colloidal 2D semiconductor nanostructures, but their synthesis remains challenging to achieve. The authors describe herein, to the best of their knowledge, the first synthesis of highly stable ZnO NPLs with the atomically precise thickness, which for the smallest NPLs is 3.2 nm (corresponding to 12 ZnO layers). Furthermore, by means of dynamic nuclear polarization-enhanced solid-state ¹⁵N NMR, the original role of the benzamidine ligands in stabilizing the surface of these nanomaterials is revealed, which can bind to both the polar and non-polar ZnO facets, acting either as X- or L-type ligands, respectively. This bimodal stabilization allows obtaining hexagonal NPLs for which the surface energy of the facets is modulated by the presence of the ligands. Thus, in-depth study of the interactions at the organic–inorganic interfaces provides a deeper understanding of the ligand–surface interface and should facilitate the future chemistry of stable-by-design nano-objects.     

Retina-Inspired Structurally Tunable Synaptic Perovskite Nanocones

Artificial photonic synapses with morphologically controlled photoreception, allowing for area-dependent tunable light reception as well as information storage and learning, have potential for application in emerging photo-interactive neuro-computing technologies. Herein, an artificially intelligent (AI) photonic synapse with area-density-tunable perovskite nano-cone arrays templated in a self-assembled block copolymer (BCP) is presented, which is based on a field effect transistor with a floating gate of photoreceptive perovskite crystal arrays preferentially synthesized in a micro-phase-segregated BCP film. These arrays are capable of electric charge (de)trapping and photo-excited charge generation, and they exhibit versatile synaptic functions of the nervous system, including paired-pulse facilitation and long-term potentiation, with excellent reliability. The area-density variable perovskite floating gate developed by off-centered spin coating process allows for emulating the human retina with a position-dependent spatial distribution of cones. 60 × 12 arrays of the developed synapse devices exhibit position-dependent dual functions of receptor and synapse. They are AI and exhibit a pattern recognition accuracy up to ≈90% when examined using the Modified National Institute of Standards and Technology handwritten digit pattern recognition test.     

Reproducible and Sensitive Plasmonic Sensing Platforms Based on Au-Nanoparticle-Internalized Nanodimpled Substrates

Electromagnetic enhancement effects through localized surface plasmon resonance considerably amplify the intensity of incident light when molecules are positioned in the vicinity of miniscule nanogaps. The aggregation of plasmonic nanoparticles synthesized using bottom-up methods has been extensively used to generate hot spots in solutions. These methods assist in obtaining non-periodic plasmonic signals, because the realization of uniform nanogaps through particle aggregation is difficult. Nanostructured substrates with gaps of 20–100 nm have also been fabricated using the top-down approach. However, the fabrication of smaller nanogap templates using these methods is difficult owing to high costs and low throughput. Therefore, a nanodimple array internalized with AuNPs is developed in this study to mitigate the challenges encountered in the bottom-up and top-down approaches. Precise nanogaps are generated by regularly internalizing AuNPs in the cavities of nanodimples through DNA hybridization. Simulations of the electric field distribution indicate that the incorporation of 80 nm-sized AuNPs into a curved nanodimpled Au substrate generate high-density volumetric hot spots within a detection volume, and result in a high plasmonic enhancement factor of 8.25 × 10⁷. The tremendous potential of the proposed plasmonic platform as an SERS-based biomedical diagnostic device is also verified.     

Assessing the helpfulness of online hotel reviews: A classification-based approach

With the rapid development of Web 2.0, travelers have started sharing their travel experiences on websites. The expanding amount of online hotel reviews results in the problem of information overload. Therefore, the effective identification of helpful reviews has become an important research issue. In this study, online hotel reviews were collected from TripAdvisor.com, and the helpfulness of these reviews was comprehensively investigated from the aspects of review quality, review sentiment, and reviewer characteristics. Review helpfulness prediction models were also developed by using classification techniques. The results indicate that reviewer characteristics are good predictors of review helpfulness, whereas review quality and review sentiment are poor predictors of review helpfulness.     

Direct Graphene Transfer and Its Application to Transfer Printing Using Mechanically Controlled,Large Area Graphene/Copper Freestanding Layer

Direct graphene transfer is an attractive candidate to prevent graphene damage, which is a critical problem of the conventional wet transfer method. Direct graphene transfer can fabricate the transferred graphene film with fewer defects by using a polymeric carrier. Here a unique direct transfer method is proposed using a 300 nm thick copper carrier as a suspended film and a transfer printing process by using the polydimethylsiloxane (PDMS) stamp under controlled peeling rate and modulus. Single and multilayer graphene are transferred to flat and curved PDMS target substrate directly. With the transfer printing process, the transfer yield of a trilayer graphene with 1000 µm s^?1 peeling rate is 68.6% of that with 1 µm s^?1 peeling rate. It is revealed that the graphene transfer yield is highly related to the storage modulus of the PDMS stamp: graphene transfer yield decreases when the storage modulus of the PDMS stamp is lower than a specific threshold value. The relationship between the graphene transfer yield and the interfacial shear strain of the PDMS stamp is studied by finite‐element method simulation and digital image correlation.     

Microstructure Controlled Porous Silicon Particles as a High Capacity Lithium Storage Material via Dual Step Pore Engineering

To overcome the lithium storage barriers of current lithium‐ion batteries, it is imperative that conventional low capacity graphite anodes be replaced with other higher capacity anode materials. Silicon is a promising alternative anode material due to its huge energy densities; however, its lithium‐concentration‐dependent volumetric changes can induce severely adverse effects that lead to drastic degradations in capacity during cycling. The dealloying of Si–metal alloys is recently suggested as a scalable approach to fabricate high‐performance porous Si anode materials. Herein, a microstructure controlled porous Si is developed by the dealloying in conjunction with wet alkaline chemical etching. The resulting 3D networked structure enables enhancement in lithium storage properties when the Si‐based material is applied not only as a single active material but also in a graphite‐blended electrode.