Outer Sphere Electron Transfer Enabling High-Voltage Aqueous Electrolytes.

Aqueous electrolytes with a low voltage window (1.23 V) and prone side reactions, such as hydrogen evolution reaction and cathode dissolution, compromise the advantages of high safety and low cost of aqueous metal-ion batteries. Herein, introducing catechol (CAT) into the aqueous electrolyte, an outer sphere electron transfer mechanism is initiated to inhibit the water reactivity, achieving an electrochemical window of 3.24 V. In a typical Zn-ion battery, the outer sphere electrons jump from CAT to Zn2+-H2O at a geometrically favorable situation and between the solvation molecules without breaking or forming chemical bonds as that of the inner sphere electron transfers. The excited state π-π stacking further leads to the outer sphere electron transfer occurring at the electrolyte/electrode interface. This high-voltage electrolyte allows achieving an operating voltage two times higher than that of the usual aqueous electrolytes and provides almost the highest energy density and power density for the V2O5-based aqueous Zn-ion full batteries. The Zn//Zn symmetric battery delivers a 4000 h lifespan, and the Zn//V2O5 full battery achieves a ∼380 W h kg-1 energy density and a 92% capacity retention after 3000 cycles at 1 A g-1 and a 2.4 V output voltage. This outer sphere electron transfer strategy paves the way for designing high-voltage aqueous electrolytes.

Large-Scale Silver Sulfide Nanomesh Membranes with Ultrahigh Flexibility.

The growth of flexible semiconductor thin films and membranes is highly desirable for the fabrication of next-generation wearable devices. In this work, we have developed a one-step, surface tension-driven method for facile and scalable growth of silver sulfide (Ag2S) membranes with a nanomesh structure. The nanomesh membrane can in principle reach infinite size but only limited by the reactor size, while the thickness is self-limited to ca. 50 nm. In particular, the membrane can be continuously regenerated at the water surface after being transferred for mechanical and electronic tests. The free-standing membrane demonstrates exceptional flexibility and strength, resulting from the nanomesh structure and the intrinsic plasticity of the Ag2S ligaments, as revealed by robust manipulation, nanoindentation tests and a pseudo-in situ tensile test under scanning electron microscope. Bendable electronic resistance-switching devices are fabricated based on the nanomesh membrane.

The Role of Structural Order in the Mechanism of Charge Transport across Tunnel Junctions with Various Iron-Storing Proteins.

In biomolecular electronics, the role of structural order in charge transport (CT) is poorly understood. It has been reported that the metal oxide cores of protein cages (e.g., iron oxide and ferrihydrite nanoparticles (NPs) present in ferritin and E2-LFtn, which is E2 protein engineered with an iron-binding sequence) play an important role in the mechanism of CT. At the same time, the NP core also plays a major role in the structural integrity of the proteins. This paper describes the role of structural order in CT across tunnel junctions by comparing three iron-storing proteins. They are (1) DNA binding protein from starved cells (Dps, diameter (∅) = 9 nm); (2) engineered archaeal ferritin (AfFtn-AA, ∅ = 12 nm); and (3) engineered E2 of pyruvate dehydrogenase enzyme complex (E2-LFtn, ∅ = 25 nm). Both holo-Dps and apo-Dps proteins undergo CT by coherent tunneling because their globular architecture and relative structural stability provide a coherent conduction pathway. In contrast, apo-AfFtn-AA forms a disordered structure across which charges have to tunnel incoherently, but holo-AfFtn-AA retains its globular structure and supports coherent tunneling. The large E2-LFtn always forms disordered structures across which charges incoherently tunnel regardless of the presence of the NP core. These findings highlight the importance of structural order in the mechanism of CT across biomolecular tunnel junctions.

Periodic nanostructures: preparation, properties and applications.

Periodic nanostructures, a group of nanomaterials consisting of single or multiple nano units/components periodically arranged into ordered patterns (e.g., vertical and lateral superlattices), have attracted tremendous attention in recent years due to their extraordinary physical and chemical properties that offer a huge potential for a multitude of applications in energy conversion, electronic and optoelectronic applications. Recent advances in the preparation strategies of periodic nanostructures, including self-assembly, epitaxy, and exfoliation, have paved the way to rationally modulate their ferroelectricity, superconductivity, band gap and many other physical and chemical properties. For example, the recent discovery of superconductivity observed in "magic-angle" graphene superlattices has sparked intensive studies in new ways, creating superlattices in twisted 2D materials. Recent development in the various state-of-the-art preparations of periodic nanostructures has created many new ideas and findings, warranting a timely review. In this review, we discuss the current advances of periodic nanostructures, including their preparation strategies, property modulations and various applications.

Role of Order in the Mechanism of Charge Transport across Single-Stranded and Double-Stranded DNA Monolayers in Tunnel Junctions.

Deoxyribonucleic acid (DNA) has been hypothesized to act as a molecular wire due to the presence of an extended π-stack between base pairs, but the factors that are detrimental in the mechanism of charge transport (CT) across tunnel junctions with DNA are still unclear. Here we systematically investigate CT across dense DNA monolayers in large-area biomolecular tunnel junctions to determine when intrachain or interchain CT dominates and under which conditions the mechanism of CT becomes thermally activated. In our junctions, double-stranded DNA (dsDNA) is 30-fold more conductive than single-stranded DNA (ssDNA). The main reason for this large change in conductivity is that dsDNA forms ordered monolayers where intrachain tunneling dominates, resulting in high CT rates. By varying the temperature T and the length of the DNA fragments in the junctions, which determines the tunneling distance, we reveal a complex interplay between T, the length of DNA, and structural order on the mechanism of charge transport. Both the increase in the tunneling distance and the decrease in structural order result in a change in the mechanism of CT from coherent tunneling to incoherent tunneling (hopping). Our results highlight the importance of the interplay between structural order, tunneling distance, and temperature on the CT mechanism across DNA in molecular junctions.

Designing Kagome Lattice from Potassium Atoms on Phosphorus-Gold Surface Alloy.

Materials with flat bands are considered as ideal platforms to explore strongly correlated physics such as the fractional quantum hall effect, high-temperature superconductivity, and more. In theory, a Kagome lattice with only nearest-neighbor hopping can give rise to a flat band. However, the successful fabrication of Kagome lattices is still very limited. Here, we provide a new design principle to construct the Kagome lattice by trapping atoms into Kagome arrays of potential valleys, which can be realized on a potassium-decorated phosphorus-gold surface alloy. Theoretical calculations show that the flat band is less correlated with the neighboring trivial electronic bands, which can be further isolated and dominate around the Fermi energy with increased Kagome lattice parameters of potassium atoms. Our results provide a new strategy for constructing Kagome lattices, which serve as an ideal platform to study topological and more general flat band phenomena.

Interfacial electronic structures revealed at the rubrene/CH3NH3PbI3 interface.

The electronic structures of rubrene films deposited on CH3NH3PbI3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward 'band bending'-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH3NH3PbI3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH3NH3PbI3 interface, its highest occupied molecular orbital (HOMO)-valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)-conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

Controllable hierarchical self-assembly: systematic study forming metallosupramolecular frameworks on the basis of helical beta-oligoamides.

Self-assembly is a key guiding principle for the design of complex nanostructures. Substituted beta oligoamides offer versatile building blocks that can have inherent folding characteristics, offering geometrically defined functionalities that can specifically bind and assemble with predefined morphological characteristics. In this work hierarchical self-assembly is implemented based on metal coordinating helical beta-oligoamides crosslinked with transition metals selected for their favourable coordination geometries, Fe2+, Cu2+, Ni2+, Co2+, Zn2+, and two metalates, MoO42-, and WO42-. The oligoamide Ac-ß3Aß3Vß3S-αHαHαH-ß3Aß3Vß3A (3H) was designed to allow crosslinking via three distinct faces of the helical unit, with a possibility of forming three dimensional framework structures. Atomic force microscopy (AFM) confirmed the formation of specific morphologies that differ characteristically with each metal. X-Ray photoelectron spectroscopy (XPS) results reveal that the metal centres can be reduced in the final structures, confirming strong chemical interaction. Time of flight secondary ion mass spectrometry (ToF-SIMS) confirmed the spatial distribution of metals within the self-assembled networks, also revealing molecular fragments that confirm coordination to histidine and carboxyl moieties. The metalates MoO42- and WO42- were also able to induce the formation of specific superstructure morphologies. It was observed that assembly with either of nickel, copper, and molybdate form thin films, while cobalt, zinc, and tungstate produced specific three dimensional networks of oligoamides. Iron was found to form both a thin film and a complex hierarchical assembly with the 3H simultaneously. The design of the 3H substituted beta oligoamide to readily form metallosupramolecular frameworks was demonstrated with a range of metals and metalates with a degree of control over layer thicknesses as a function of the metal/metalate. The results validate and broaden the metallosupramolecular framework concept and establish a platform technology for the design of functional thin layer materials.

Highly Sensitive NO2 Gas Sensors Based on MoS2@MoO3 Magnetic Heterostructure.

Recently, two-dimensional (2D) materials and their heterostructures have attracted considerable attention in gas sensing applications. In this work, we synthesized 2D MoS2@MoO3 heterostructures through post-sulfurization of α-MoO3 nanoribbons grown via vapor phase transport (VPT) and demonstrated highly sensitive NO2 gas sensors based on the hybrid heterostructures. The morphological, structural, and compositional properties of the MoS2@MoO3 hybrids were studied by a combination of advanced characterization techniques revealing a core-shell structure with the coexistence of 2H-MoS2 multilayers and intermediate molybdenum oxysulfides on the surface of α-MoO3. The MoS2@MoO3 hybrids also exhibit room-temperature ferromagnetism, revealed by vibrating sample magnetometry (VSM), as a result of the sulfurization process. The MoS2@MoO3 gas sensors display a p-type-like response towards NO2 with a detection limit of 0.15 ppm at a working temperature of 125 °C, as well as superb selectivity and reversibility. This p-type-like sensing behavior is attributed to the heterointerface of MoS2-MoO3 where interfacial charge transfer leads to a p-type inversion layer in MoS2, and is enhanced by magnetic dipole interactions between the paramagnetic NO2 and the ferromagnetic sensing layer. Our study demonstrates the promising application of 2D molybdenum hybrid compounds in gas sensing applications with a unique combination of electronic and magnetic properties.

Liquid metal derived MOF functionalized nanoarrays with ultra-wideband electromagnetic absorption.

Low melting point liquid metal alloys are progressively utilized in different research fields due to their unique physicochemical properties. Among them, EGaIn is liquid at room temperature with an excellent solubility for reactive metal atoms such as Al. Combined with their characteristic flexible surface, large area and atomically flat interfaces, a library of two-dimensional materials can be generated. Liquid metal synthesis routes provide a highly reproducible thickness of nanosheets with fast, simple, scalable, inexpensive, high yield and non-toxic methods, especially for Al oxides and hydroxides. At the same time, Al-based heterojunction structure also shows a good application prospect in the field of electromagnetic wave absorption, therefore, the use of liquid metal synthesis methods to find the synthesis methods of Al-based layered double hydroxide (LDH) and its derivatives remains to be explored. In this work, EGaIn was used as an aluminum reservoir to prepare LDH and metal organic framework (MOFs) nano-arrays. The prepared CoAl-LDH@ZIF 67 can be transformed into CoAl-LDO@Co-C in the subsequent annealing process performed under nitrogen environments. Interestingly, a series of samples with different morphologies can be obtained by changing the synthesis parameters. The excellent electromagnetic wave interactions are fully characterized. It has an effective absorption bandwidth of 8.48 GHz at 2.6 mm. The findings demonstrated in this work pave the way for the application of lightwave and ductile complex nanoarrays obtained from liquid metals.

Negative tunneling magnetoresistance by canted magnetization in MgO/NiO tunnel barriers.

The influence of the insertion of an ultrathin NiO layer between the MgO barrier and the ferromagnetic electrodes in magnetic tunnel junctions has been investigated from measurements of the tunneling magnetoresistance and via x-ray magnetic circular dichroism (XMCD). The magnetoresistance shows a high asymmetry with respect to bias voltage, giving rise to a negative value of up to -16% at 2.8 K. We attribute this effect to the formation of noncollinear spin structures at the interface of the NiO layer as inferred from XMCD measurements. The magnetic moments of the interface Ni atoms tilt from their easy axis due to exchange coupling with the neighboring ferromagnetic electrode, and the tilting angle decreases with increasing NiO thickness. The experimental observations are further supported by noncollinear spin density functional calculations.

A synchrotron-based photoemission study of the MoO3∕Co interface.

The electronic structures at the MoO(3)∕Co interface were investigated using synchrotron-based ultraviolet and x-ray photoelectron spectroscopy. It was found that interfacial chemical reactions lead to the reduction of Mo oxidation states and the formation of Co-O bonds. These interfacial chemical reactions also induce a large interface dipole, which significantly increases the work function of the cobalt substrate. In addition, two interface states located at 1.0 and 2.0 eV below the Fermi level are identified. These two states overlap at film thickness of between 2-4 nm, which suggests the MoO(3) intermediate layer may facilitate ohmic charge transport.

Charge transfer dynamics of 3,4,9,10-perylene-tetracarboxylic-dianhydride molecules on Au(111) probed by resonant photoemission spectroscopy.

Charge transfer dynamics across the lying-down 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) organic semiconductor molecules on Au(111) interface has been investigated using the core-hole clock implementation of resonant photoemission spectroscopy. It is found that the charge transfer time scale at the PTCDA∕Au(111) interface is much larger than the C 1s core-hole lifetime of 6 fs, indicating weak electronic coupling between PTCDA and the gold substrate due to the absence of chemical reaction and∕or bonding.

Wide Bandgap Oxide Semiconductors: from Materials Physics to Optoelectronic Devices.

Wide bandgap oxide semiconductors constitute a unique class of materials that combine properties of electrical conductivity and optical transparency. They are being widely used as key materials in optoelectronic device applications, including flat-panel displays, solar cells, OLED, and emerging flexible and transparent electronics. In this article, an up-to-date review on both the fundamental understanding of materials physics of oxide semiconductors, and recent research progress on design of new materials and high-performing thin film transistor (TFT) devices in the context of fundamental understanding is presented. In particular, an in depth overview is first provided on current understanding of the electronic structures, defect and doping chemistry, optical and transport properties of oxide semiconductors, which provide essential guiding principles for new material design and device optimization. With these principles, recent advances in design of p-type oxide semiconductors, new approaches for achieving cost-effective transparent (flexible) electrodes, and the creation of high mobility 2D electron gas (2DEG) at oxide surfaces and interfaces with a wealth of fascinating physical properties of great potential for novel device design are then reviewed. Finally, recent progress and perspective of oxide TFT based on new oxide semiconductors, 2DEG, and low-temperature solution processed oxide semiconductor for flexible electronics will be reviewed.

Enhanced Metal-Insulator Transition in Freestanding VO2 Down to 5 nm Thickness.

Ultrathin freestanding membranes with a pronounced metal-insulator transition (MIT) have huge potential for future flexible electronic applications as well as provide a unique aspect for the study of lattice-electron interplay. However, the reduction of the thickness to an ultrathin region (a few nm) is typically detrimental to the MIT in epitaxial films, and even catastrophic for their freestanding form. Here, we report an enhanced MIT in VO2-based freestanding membranes, with a lateral size up to millimeters and the VO2 thickness down to 5 nm. The VO2 membranes were detached by dissolving a Sr3Al2O6 sacrificial layer between the VO2 thin film and the c-Al2O3(0001) substrate, allowing the transfer onto arbitrary surfaces. Furthermore, the MIT in the VO2 membrane was greatly enhanced by inserting an intermediate Al2O3 buffer layer. In comparison with the best available ultrathin VO2 membranes, the enhancement of MIT is over 400% at a 5 nm VO2 thickness and more than 1 order of magnitude for VO2 above 10 nm. Our study widens the spectrum of functionality in ultrathin and large-scale membranes and enables the potential integration of MIT into flexible electronics and photonics.

Bias-Polarity-Dependent Direct and Inverted Marcus Charge Transport Affecting Rectification in a Redox-Active Molecular Junction.

This paper describes the transition from the normal to inverted Marcus region in solid-state tunnel junctions consisting of self-assembled monolayers of benzotetrathiafulvalene (BTTF), and how this transition determines the performance of a molecular diode. Temperature-dependent normalized differential conductance analyses indicate the participation of the HOMO (highest occupied molecular orbital) at large negative bias, which follows typical thermally activated hopping behavior associated with the normal Marcus regime. In contrast, hopping involving the HOMO dominates the mechanism of charge transport at positive bias, yet it is nearly activationless indicating the junction operates in the inverted Marcus region. Thus, within the same junction it is possible to switch between Marcus and inverted Marcus regimes by changing the bias polarity. Consequently, the current only decreases with decreasing temperature at negative bias when hopping is "frozen out," but not at positive bias resulting in a 30-fold increase in the molecular rectification efficiency. These results indicate that the charge transport in the inverted Marcus region is readily accessible in junctions with redox molecules in the weak coupling regime and control over different hopping regimes can be used to improve junction performance.

The supramolecular structure and van der Waals interactions affect the electronic structure of ferrocenyl-alkanethiolate SAMs on gold and silver electrodes.

Understanding the influence of structural properties on the electronic structure will pave the way for optimization of charge transport properties of SAM devices. In this study, we systematically investigate the supramolecular and electronic structures of ferrocene (Fc) terminated alkanethiolate (SC n Fc) SAMs on both Au and Ag substrates with n = 1-15 by using a combination of synchrotron based near edge X-ray absorption spectroscopy (NEXAFS), photoemission spectroscopy (PES), and density functional theory (DFT) calculations. Odd-even effects in the supramolecular structure persist over the entire range of n = 1-15, which, in turn, explain the odd-even effects in the onset energy of the highest occupied molecular (HOMO) orbital. The orientation of the Fc moieties and the strength of Fc-substrate coupling, which both depend on n, affects the work function (WF). The variation of WF shows an odd-even effect in the weak electrode-Fc coupling regime for n ≥ 8, whereas the odd-even effect diminishes for n < 8 due to hybridization between Fc and the electrode (n < 3) or van der Waals (vdW) interactions between Fc and the electrode (n = 3-7). These results confirm that subtle changes in the supramolecular structure of the SAMs cause significant electronic changes that have a large influence on device properties.

An Fe stabilized metallic phase of NiS2 for the highly efficient oxygen evolution reaction.

This work reports a fundamental study on the relationship of the electronic structure, catalytic activity and surface reconstruction process of Fe doped NiS2 (FexNi1-xS2) for the oxygen evolution reaction (OER). A combined photoemission and X-ray absorption spectroscopic study reveals that Fe doping introduces more occupied Fe 3d6 states at the top of the valence band and thereby induces a metallic phase. Meanwhile, Fe doping also significantly increases the OER activity and results in much better stability with the optimum found for Fe0.1Ni0.9S2. More importantly, we performed detailed characterization to track the evolution of the structure and composition of the catalysts after different cycles of OER testing. Our results further confirmed that the catalysts gradually transform into amorphous (oxy)hydroxides which are the actual active species for the OER. However, a fast phase transformation in NiS2 is accompanied by a decrease of OER activity, because of the formation of a thick insulating NiOOH layer limiting electron transfer. On the other hand, Fe doping retards the process of transformation, because of a shorter Fe-S bond length (2.259 Å) than Ni-S (2.400 Å), explaining the better electrochemical stability of Fe0.1Ni0.9S2. These results suggest that the formation of a thin surface layer of NiFe (oxy)hydroxide as an active OER catalyst and the remaining Fe0.1Ni0.9S2 as a conductive core for fast electron transfer is the base for the high OER activity of FexNi1-xS2. Our work provides important insight and design principle for metal chalcogenides as highly active OER catalysts.

Is Charge-Transfer Doping Possible at the Interfaces of Monolayer VSe2 with MoO3 and K?

Being a metallic transition-metal dichalcogenide, monolayer vanadium diselenide (VSe2) exhibits many novel properties, such as charge density waves and magnetism. Its interfaces with other materials can potentially be used in device applications as well as for manipulating its intrinsic properties. Here, we present a scanning tunneling microscopy and synchrotron-based X-ray photoemission spectroscopy study of the surface charge-transfer doping using efficient electron-withdrawing and electron-donating materials, that is, molybdenum trioxide (MoO3) and potassium (K), on the molecular beam epitaxy-grown monolayer VSe2 on highly oriented pyrolytic graphite (HOPG). We demonstrate that monolayer VSe2 is immune to MoO3- and K-doping effects. However, at the monolayer edges where the local chemical reactivity is higher because of Se deficiency, MoO3 is seen to react with VSe2 to form molybdenum dioxide (MoO2) and vanadium dioxide (VO2). Compared to the obvious charge-transfer doping effects of MoO3 and K on HOPG, the electronic structure of monolayer VSe2 is barely perturbed. This is attributed to the large density of states at the Fermi level of monolayer VSe2 carrying the metallic character. This work provides new insights into the chemical and electronic properties of monolayer VSe2, important for future VSe2-based electronic device design.

Orbital dependent ultrafast charge transfer dynamics of ferrocenyl-functionalized SAMs on gold studied by core-hole clock spectroscopy.

Understanding the charge transport properties in general of different molecular components in a self-assembled monolayer (SAM) is of importance for the rational design of SAM molecular structures for molecular electronics. In this study, we study an important aspect of the charge transport properties, i.e. the charge transfer (CT) dynamics between the active molecular component (in this case, the ferrocenyl moieties of a ferrocenyl-n-alkanethiol SAM) and the electrode using synchrotron-based core-hole clock (CHC) spectroscopy. The characteristic CT times are found to depend strongly on the character of the ferrocenyl-derived molecular orbitals (MOs) which mediate the CT process. Furthermore, by systemically shifting the position of the ferrocenyl moiety in the SAM, it is found that the CT characteristics of the ferrocenyl MOs display distinct dependence on its distance to the electrode. These results demonstrate experimentally that the efficiency and rate of charge transport through the molecular backbone can be modulated by resonant injection of charge carriers into specific MOs.