Self‐Organized Epitaxial Vertically Aligned Nanocomposites with Long‐Range Ordering Enabled by Substrate Nanotemplating

Vertically aligned nanocomposites (VAN) thin films present as an intriguing material family for achieving novel functionalities. However, most of the VAN structures tend to grow in a random fashion, hindering the future integration in nanoscale devices. Previous efforts for achieving ordered nanopillar structures have been focused on specific systems, and rely on sophisticated lithography and seeding techniques, making large area ordering quite difficult. In this work, a new technique is presented to produce self‐assembled nanocomposites with long‐range ordering through selective nucleation of nanocomposites on termination patterned substrates. Specifically, SrTiO₃ (001) substrates have been annealed to achieve alternating chemical terminations and thus enable selective epitaxy during the VAN growth. La_0.7Sr_0.3MnO₃:CeO₂ (LSMO):CeO₂ nanocomposites, as a prototype, are demonstrated to form well‐ordered rows in matrix structure, with CeO₂ (011) domains selectively grown on SrO terminated area, showing enhanced functionality. This approach provides a large degree of long‐range ordering for nanocomposite growth that could lead to unique functionalities and takes the nanocomposites one step closer toward future nanoscale device integration.     

Band‐Gap Engineering at a Semiconductor–Crystalline Oxide Interface

The epitaxial growth of crystalline oxides on semiconductors provides a pathway to introduce new functionalities to semiconductor devices. Key to electrically coupling crystalline oxides with semiconductors to realize functional behavior is to control the manner in which their bands align at interfaces. Here, principles of band‐gap engineering traditionally used at heterojunctions between conventional semiconductors are applied to control the band offset between a single crystalline oxide and a semiconductor. Reactive molecular beam epitaxy is used to realize atomically abrupt and structurally coherent interfaces between SrZr_xTi_1−xO₃ and Ge, in which the band‐gap of the former is enhanced with Zr content x. Structural and electrical characterization of SrZr_xTi_1−xO₃‐Ge heterojunctions for x = 0.2 to 0.75 are presented and it is demonstrated that the band offset can be tuned from type‐II to type‐I, with the latter being verified using photoemission measurements. The type‐I band offset provides a platform to integrate the dielectric, ferroelectric, and ferromagnetic functionalities of oxides with semiconducting devices.     

Metal‐Organic Frameworks for CO2 Chemical Transformations

Carbon dioxide (CO₂), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO₂ into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal‐organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure‐function relationships for transforming CO₂ into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO₂. Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area.     

O3‐Type Layered Ni‐Rich Oxide: A High‐Capacity and Superior‐Rate Cathode for Sodium‐Ion Batteries

Inspired by its high‐active and open layered framework for fast Li⁺ extraction/insertion reactions, layered Ni‐rich oxide is proposed as an outstanding Na‐intercalated cathode for high‐performance sodium‐ion batteries. An O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ is achieved through a facile electrochemical ion‐exchange strategy in which Li⁺ ions are first extracted from the LiNi_0.82Co_0.12Mn_0.06O₂ cathode and Na⁺ ions are then inserted into a layered oxide framework. Furthermore, the reaction mechanism of layered Ni‐rich oxide during Na⁺ extraction/insertion is investigated in detail by combining ex situ X‐ray diffraction, X‐ray photoelectron spectroscopy, and electron energy loss spectroscopy. As an excellent cathode for Na‐ion batteries, O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ delivers a high reversible capacity of 171 mAh g^?1 and a remarkably stable discharge voltage of 2.8 V during long‐term cycling. In addition, the fast Na⁺ transport in the cathode enables high rate capability with 89 mAh g^?1 at 9 C. The as‐prepared Ni‐rich oxide cathode is expected to significantly break through the limited performance of current sodium‐ion batteries.     

Self‐Assembly of Enzyme‐Like Nanofibrous G‐Molecular Hydrogel for Printed Flexible Electrochemical Sensors

Conducting hydrogels provide great potential for creating designer shape‐morphing architectures for biomedical applications owing to their unique solid–liquid interface and ease of processability. Here, a novel nanofibrous hydrogel with significant enzyme‐like activity that can be used as “ink” to print flexible electrochemical devices is developed. The nanofibrous hydrogel is self‐assembled from guanosine (G) and KB(OH)₄ with simultaneous incorporation of hemin into the G‐quartet scaffold, giving rise to significant enzyme‐like activity. The rapid switching between the sol and gel states responsive to shear stress enables free‐form fabrication of different patterns. Furthermore, the replication of the G‐quartet wires into a conductive matrix by in situ catalytic deposition of polyaniline on nanofibers is demonstrated, which can be directly printed into a flexible electrochemical electrode. By loading glucose oxidase into this novel hydrogel, a flexible glucose biosensor is developed. This study sheds new light on developing artificial enzymes with new functionalities and on fabrication of flexible bioelectronics.     

Label‐Free Optofluidic Nanobiosensor Enables Real‐Time Analysis of Single‐Cell Cytokine Secretion

Single‐cell analysis of cytokine secretion is essential to understand the heterogeneity of cellular functionalities and develop novel therapies for multiple diseases. Unraveling the dynamic secretion process at single‐cell resolution reveals the real‐time functional status of individual cells. Fluorescent and colorimetric‐based methodologies require tedious molecular labeling that brings inevitable interferences with cell integrity and compromises the temporal resolution. An innovative label‐free optofluidic nanoplasmonic biosensor is introduced for single‐cell analysis in real time. The nanobiosensor incorporates a novel design of a multifunctional microfluidic system with small volume microchamber and regulation channels for reliable monitoring of cytokine secretion from individual cells for hours. Different interleukin‐2 secretion profiles are detected and distinguished from single lymphoma cells. The sensor configuration combined with optical spectroscopic imaging further allows us to determine the spatial single‐cell secretion fingerprints in real time. This new biosensor system is anticipated to be a powerful tool to characterize single‐cell signaling for basic and clinical research.     

Tunable Polarity Behavior and Self‐Driven Photoswitching in p‐WSe2/n‐WS2 Heterojunctions

Van der Waals (vdW) p–n heterojunctions consisting of various 2D layer compounds are fascinating new artificial materials that can possess novel physics and functionalities enabling the next‐generation of electronics and optoelectronics devices. Here, it is reported that the WSe₂/WS₂ p–n heterojunctions perform novel electrical transport properties such as distinct rectifying, ambipolar, and hysteresis characteristics. Intriguingly, the novel tunable polarity transition along a route of n‐“anti‐bipolar”–p‐ambipolar is observed in the WSe₂/WS₂ heterojunctions owing to the successive work of conducting channels of junctions, p‐WSe₂ and n‐WS₂ on the electrical transport of the whole systems. The type‐II band alignment obtained from first principle calculations and built‐in potential in this vdW heterojunction can also facilitate the efficient electron–hole separation, thus enabling the significant photovoltaic effect and a much enhanced self‐driven photoswitching response in this system.     

Metal–Organic Framework Hybrid‐Assisted Formation of Co3O4/Co‐Fe Oxide Double‐Shelled Nanoboxes for Enhanced Oxygen Evolution

Rational design of complex metal–organic framework (MOF) hybrid precursors offers a great opportunity to construct various functional nanostructures. Here, a novel MOF‐hybrid‐assisted strategy to synthesize Co₃O₄/Co‐Fe oxide double‐shelled nanoboxes is reported. In the first step, zeolitic imidazolate framework‐67 (ZIF‐67, a Co‐based MOF)/Co‐Fe Prussian blue analogue (PBA) yolk–shell nanocubes are formed via a facile anion‐exchange reaction between ZIF‐67 nanocube precursors and [Fe(CN)₆]^3? ions at room temperature. Subsequently, an annealing treatment is applied to prepare Co₃O₄/Co‐Fe oxide double‐shelled nanoboxes. Owing to the structural and compositional benefits, the as‐derived Co₃O₄/Co‐Fe oxide double‐shelled nanoboxes exhibit enhanced electrocatalytic performance for oxygen evolution reaction in alkaline solution.     

Ultrastable Supramolecular Self‐Encapsulated Wide‐Bandgap Conjugated Polymers for Large‐Area and Flexible Electroluminescent Devices

Controlling chain behavior through smart molecular design provides the potential to develop ultrastable and efficient deep‐blue light‐emitting conjugated polymers (LCPs). Herein, a novel supramolecular self‐encapsulation strategy is proposed to construct a robust ultrastable conjugated polydiarylfluorene (PHDPF‐Cz) via precisely preventing excitons from interchain cross‐transfer/coupling and contamination from external trace H₂O/O₂. PHDPF‐Cz consists of a mainchain backbone where the diphenyl groups localize at the 9‐position as steric bulk moieties, and carbazole (Cz) units localize at the 4‐position as supramolecular π‐stacked synthon with the dual functionalities of self‐assembly capability and hole‐transport facility. The synergistic effect of the steric bulk groups and π‐stacked carbazoles affords PHDPF‐Cz as an ultrastable property, including spectral, morphological stability, and storage stability. In addition, PHDPF‐Cz spin‐coated gelation films also show thickness‐insensitive deep‐blue emission with respect to the reference polymers, which are suitable to construct solution‐processed large‐scale optoelectronic devices with higher reproducibility. High‐quality and uniform deep‐blue emission is observed in large‐area solution‐processed films. The electroluminescence shows high‐quality deep‐blue intrachain emission with a CIE (0.16, 0.12) and a very narrow full width at half‐maximum of 32 nm. Finally, large‐area and flexible polymer light‐emitting devices with a single‐molecular excitonic behavior are also fabricated. The supramolecular self‐encapsulation design provides an effective strategy to construct ultrastable LCPs for optoelectronic applications.     

Self‐Assembled Ordered Three‐Phase Au–BaTiO3–ZnO Vertically Aligned Nanocomposites Achieved by a Templating Method

Complex multiphase nanocomposite designs present enormous opportunities for developing next‐generation integrated photonic and electronic devices. Here, a unique three‐phase nanostructure combining a ferroelectric BaTiO₃, a wide‐bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two‐step templated growth, a highly ordered Au–BaTiO₃–ZnO nanocomposite in a unique “nanoman”‐like form, i.e., self‐assembled ZnO nanopillars and Au nanopillars in a BaTiO₃ matrix, is realized, and is very different from the random three‐phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO₃ matrix. The ordered three‐phase “nanoman”‐like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near‐infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self‐assembled and ordered three‐phase nanocomposite is obtained through a combination of vapor–liquid–solid (VLS) and two‐phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron–light–matter interactions at the nanoscale.     

Framework‐Porphyrin‐Derived Single‐Atom Bifunctional Oxygen Electrocatalysts and their Applications in Zn–Air Batteries

High‐performance bifunctional oxygen electrocatalysis constitutes the key technique for the widespread application of clean and sustainable energy through electrochemical devices such as rechargeable Zn–air batteries. Single‐atom electrocatalysts with maximum atom efficiency are highly considered as an alternative of the present noble‐metal‐based electrocatalysts. However, the fabrication of transition metal single‐atoms is very challenging, requiring extensive attempts of precursors with novel design principles. Herein, an all‐covalently constructed cobalt‐coordinated framework porphyrin with graphene hybridization is innovatively designed and prepared as the pyrolysis precursor to fabricate single‐atom Co–N_x–C electrocatalysts. Excellent electrochemical performances are realized for both bifunctional oxygen electrocatalysis and rechargeable Zn–air batteries with regard to reduced overpotentials, improved kinetics, and prolonged cycling stability comparable with noble‐metal‐based electrocatalysts. Design principles from multiple scales are proposed and rationalized with detailed mechanism investigation. This work not only provides a novel precursor for the fabrication of high‐performance single‐atom electrocatalysts, but also inspires further attempts to develop advanced materials and emerging applications.     

Ultrahigh‐Sensitive Broadband Photodetectors Based on Dielectric Shielded MoTe2/Graphene/SnS2 p–g–n Junctions

2D atomic sheets of transition metal dichalcogenides (TMDs) have a tremendous potential for next‐generation optoelectronics since they can be stacked layer‐by‐layer to form van der Waals (vdW) heterostructures. This allows not only bypassing difficulties in heteroepitaxy of lattice‐mismatched semiconductors of desired functionalities but also providing a scheme to design new optoelectronics that can surpass the fundamental limitations on their conventional semiconductor counterparts. Herein, a novel 2D h‐BN/p‐MoTe₂/graphene/n‐SnS₂/h‐BN p–g–n junction, fabricated by a layer‐by‐layer dry transfer, demonstrates high‐sensitivity, broadband photodetection at room temperature. The combination of the MoTe₂ and SnS₂ of complementary bandgaps, and the graphene interlayer provides a unique vdW heterostructure with a vertical built‐in electric field for high‐efficiency broadband light absorption, exciton dissociation, and carrier transfer. The graphene interlayer plays a critical role in enhancing sensitivity and broadening the spectral range. An optimized device containing 5?7‐layer graphene has been achieved and shows an extraordinary responsivity exceeding 2600 A W^?1 with fast photoresponse and specific detectivity up to ≈10¹³ Jones in the ultraviolet–visible–near‐infrared spectrum. This result suggests that the vdW p–g–n junctions containing multiple photoactive TMDs can provide a viable approach toward future ultrahigh‐sensitivity and broadband photonic detectors.     

Electrochromic materials using mechanically interlocked molecules

Recent investigations on the design and synthesis of electrochromic materials based on switchable three-station [2]catenanes are summarized. The reasoning and preliminary experiments behind the design of electrochemically controllable red–green–blue (RGB), donor–acceptor [2]catenanes are presented. A basis for color generation is discussed in which the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), serves as the π-electron deficient ring which circumrotates between three π-electron rich recognition sites within a macrocyclic polyether, generating the three different colors (RGB) based on the different charge transfer interactions between the tetracationic cyclophane and recognition sites based on 1,5-dioxynaphthalene (R), tetrathiafulvalene (G) and benzidine (B). Issues relating to the realization of an RGB [2]catenane are raised and discussed: they include (i) color tuning, (ii) thermodynamic considerations, (iii) electrochemistry on model compounds, (iv) molecular design, (v) the electrochemical behavior of three-station [2]catenanes and (vi) electrochromism in polymer gel matrices. Finally, the challenges that need to be met in the future if the ideal RGB catenane is to be prepared, are outlined.     

Self‐Folded Gripper‐Like Architectures from Stimuli‐Responsive Bilayers

Self‐folding microgrippers are an emerging class of smart structures that have widespread applications in medicine and micro/nanomanipulation. To achieve their functionalities, these architectures rely on spatially patterned hinges to transform into 3D configurations in response to an external stimulus. Incorporating hinges into the devices requires the processing of multiple layers which eventually increases the fabrication costs and actuation complexities. The goal of this work is to demonstrate that it is possible to achieve gripper‐like configurations in an on‐demand manner from simple planar bilayers that do not require hinges for their actuation. Finite element modeling of bilayers is performed to understand the mechanics behind their stimuli‐responsive shape transformation behavior. The model predictions are then experimentally validated and axisymmetric gripper‐like shapes are realized using millimeter‐scale poly(dimethylsiloxane) bilayers that undergo differential swelling in organic solvents. Owing to the nature of the computational scheme which is independent of length scales and material properties, the guidelines reported here would be applicable to a diverse array of gripping systems and functional devices. Thus, this work not only demonstrates a simple route to fabricate functional microgrippers but also contributes to self‐assembly in general.     

Electrochromic materials using mechanically interlocked molecules

Abstract

Recent investigations on the design and synthesis of electrochromic materials based on switchable three-station [2]catenanes are summarized. The reasoning and preliminary experiments behind the design of electrochemically controllable red–green–blue (RGB), donor–acceptor [2]catenanes are presented. A basis for color generation is discussed in which the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), serves as the π-electron deficient ring which circumrotates between three π-electron rich recognition sites within a macrocyclic polyether, generating the three different colors (RGB) based on the different charge transfer interactions between the tetracationic cyclophane and recognition sites based on 1,5-dioxynaphthalene (R), tetrathiafulvalene (G) and benzidine (B). Issues relating to the realization of an RGB [2]catenane are raised and discussed: they include (i) color tuning, (ii) thermodynamic considerations, (iii) electrochemistry on model compounds, (iv) molecular design, (v) the electrochemical behavior of three-station [2]catenanes and (vi) electrochromism in polymer gel matrices. Finally, the challenges that need to be met in the future if the ideal RGB catenane is to be prepared, are outlined.     

A Lithography‐Free and Field‐Programmable Photonic Metacanvas

The unique correspondence between mathematical operators and photonic elements in wave optics enables quantitative analysis of light manipulation with individual optical devices. Phase‐transition materials are able to provide real‐time reconfigurability of these devices, which would create new optical functionalities via (re)compilation of photonic operators, as those achieved in other fields such as field‐programmable gate arrays (FPGA). Here, by exploiting the hysteretic phase transition of vanadium dioxide, an all‐solid, rewritable metacanvas on which nearly arbitrary photonic devices can be rapidly and repeatedly written and erased is presented. The writing is performed with a low‐power laser and the entire process stays below 90 °C. Using the metacanvas, dynamic manipulation of optical waves is demonstrated for light propagation, polarization, and reconstruction. The metacanvas supports physical (re)compilation of photonic operators akin to that of FPGA, opening up possibilities where photonic elements can be field programmed to deliver complex, system‐level functionalities.     

Design of order‐preserving algorithms for transient first‐order systems with controllable numerical dissipation

Using a new design procedure termed as Algorithms by Design, which we have successfully introduced in our previous efforts for second‐order systems, alternatively, we advance in this exposition, the design and development of a computational framework that permits order‐preserving second‐order time accurate, unconditionally stable, zero‐order overshooting behavior, and features with controllable numerical dissipation and dispersion via a family of algorithms for effectively solving transient first‐order systems. The key feature is the incorporation of a spurious root to introduce controllable numerical dissipation while preserving second‐order accuracy (order‐preserving feature) resulting in a two‐root system, namely, the principal root (ρ_1∞) and a spurious root (ρ_2∞). In contrast to the classical Trapezoidal family of algorithms which are the most popular, the present framework has the same order of computational complexity, but a higher payoff that is a significant advance to the field for tackling a wide class of applications dealing with first‐order transient systems. We also present the special case with selection of ρ_1∞ = 1 and any ρ_2∞ leading to the design of a family of generalized single‐step single‐solve [GS4‐1] algorithms recovering the Crank–Nicolson method at one end (ρ_2∞ = 1) and the Midpoint Rule at the other end (ρ_2∞ = 0) and anything in between, all of which have spectral radius features resembling that of the Crank–Nicolson method. More interestingly, with the particular choice of ρ_1∞ = ρ_2∞ = 0, the developed framework additionally inherits L‐stable features. We illustrate the successful design of the developed GS4‐1 framework using two simple illustrative numerical examples. Copyright © 2011 John Wiley & Sons, Ltd.     

Exposing {001} Crystal Plane on Hexagonal Ni‐MOF with Surface‐Grown Cross‐Linked Mesh‐Structures for Electrochemical Energy Storage

Hexagonal nickel‐organic framework (Ni‐MOF) [Ni(NO₃)₂·6H₂O, 1,3,5‐benzenetricarboxylic acid, 4‐4′‐bipyridine] is fabricated through a one‐step solvothermal method. The {001} crystal plane is exposed to the largest hexagonal surface, which is an ideal structure for electron transport and ion diffusion. Compared with the surrounding rectangular crystal surface, the ion diffusion length through the {001} crystal plane is the shortest. In addition, the cross‐linked porous mesh structures growing on the {001} crystal plane strengthen the mixing with conductive carbon, inducing preferable conductivity, as well as increasing the area of ion contact and the number of active sites. These advantages enable the hexagonal Ni‐MOF to exhibit excellent electrochemical performance as supercapacitor electrode materials. In a three‐electrode cell, specific capacitance of hexagonal Ni‐MOF in the 3.0 m KOH electrolyte is 977.04 F g^?1 and remains at the initial value of 92.34% after 5,000 cycles. When the hexagonal Ni‐MOF and activated carbon are assembled into aqueous devices, the electrochemical performance remains effective.     

Graphene Scroll‐Coated α‐MnO2 Nanowires as High‐Performance Cathode Materials for Aqueous Zn‐Ion Battery

The development of manganese dioxide as the cathode for aqueous Zn‐ion battery (ZIB) is limited by the rapid capacity fading and material dissolution. Here, a highly reversible aqueous ZIB using graphene scroll‐coated α‐MnO₂ as the cathode is proposed. The graphene scroll is uniformly coated on the MnO₂ nanowire with an average width of 5 nm, which increases the electrical conductivity of the MnO₂ nanowire and relieves the dissolution of the cathode material during cycling. An energy density of 406.6 Wh kg^?1 (382.2 mA h g^?1) at 0.3 A g^?1 can be reached, which is the highest specific energy value among all the cathode materials for aqueous Zn‐ion battery so far, and good long‐term cycling stability with 94% capacity retention after 3000 cycles at 3 A g^?1 are achieved. Meanwhile, a two‐step intercalation mechanism that Zn ions first insert into the layers and then the tunnels of MnO₂ framework is proved by in situ X‐ray diffraction, galvanostatic intermittent titration technique, and X‐ray photoelectron spectroscopy characterizations. The graphene scroll‐coated metallic oxide strategy can also bring intensive interests for other energy storage systems.     

Solution Processed Metal Oxide High‐κ Dielectrics for Emerging Transistors and Circuits

The electronic functionalities of metal oxides comprise conductors, semiconductors, and insulators. Metal oxides have attracted great interest for construction of large‐area electronics, particularly thin‐film transistors (TFTs), for their high optical transparency, excellent chemical and thermal stability, and mechanical tolerance. High‐permittivity (κ) oxide dielectrics are a key component for achieving low‐voltage and high‐performance TFTs. With the expanding integration of complementary metal oxide semiconductor transistors, the replacement of SiO₂ with high‐κ oxide dielectrics has become urgently required, because their provided thicker layers suppress quantum mechanical tunneling. Toward low‐cost devices, tremendous efforts have been devoted to vacuum‐free, solution processable fabrication, such as spin coating, spray pyrolysis, and printing techniques. This review focuses on recent progress in solution processed high‐κ oxide dielectrics and their applications to emerging TFTs. First, the history, basics, theories, and leakage current mechanisms of high‐κ oxide dielectrics are presented, and the underlying mechanism for mobility enhancement over conventional SiO₂ is outlined. Recent achievements of solution‐processed high‐κ oxide materials and their applications in TFTs are summarized and traditional coating methods and emerging printing techniques are introduced. Finally, low temperature approaches, e.g., ecofriendly water‐induced, self‐combustion reaction, and energy‐assisted post treatments, for the realization of flexible electronics and circuits are discussed.