Large Electromechanical Response in a Polycrystalline Alkali-Deficient (K,Na)NbO3 Thin Film on Silicon.

The demand for large electromechanical performance in lead-free polycrystalline piezoelectric thin films is driven by the need for compact, high-performance microelectromechanical systems (MEMS) based devices operating at low voltages. Here we significantly enhance the electromechanical response in a polycrystalline lead-free oxide thin film by utilizing lattice-defect-induced structural inhomogeneities. Unlike prior observations in mismatched epitaxial films with limited low-frequency enhancements, we achieve large electromechanical strain in a polycrystalline (K,Na)NbO3 film integrated on silicon. This is achieved by inducing self-assembled Nb-rich planar faults with a nonstoichiometric composition. The film exhibits an effective piezoelectric coefficient of 565 pm V-1 at 1 kHz, surpassing those of lead-based counterparts. Notably, lattice defect growth is substrate-independent, and the large electromechanical response is extended to even higher frequencies in a polycrystalline film. Improved properties arise from unique lattice defect morphology and frequency-dependent relaxation behavior, offering a new route to remarkable electromechanical response in polycrystalline thin films.

Galvanic corrosion protection of Al-alloy in contact with carbon fibre reinforced polymer through plasma electrolytic oxidation treatment.

Al-alloy/carbon fibre reinforced polymer (CFRP) joint systems offer exceptionally lightweight, superior fatigue behaviour and impact resistance for aerospace applications. Nevertheless, the galvanic corrosion at the joint interfaces accelerates the adhesive failure and strength damage. In this work, oxidation of Al 7075 alloy was studied by employing plasma electrolytic oxidation (PEO) and thin film sulphuric acid anodizing (TFSAA) methods, addressing their galvanic corrosion (GC) protection performance in contact with CFRP. Structural and electrochemical characterisations were carried out in tandem with varied oxidation process parameters, revealing that high voltage PEO resulted in crystallized compact ceramic coating and thus improved GC protection. A decrease in the GC current by ~ 90% has been achieved by using the PEO coating at 700 V compared with the ~ 12% current reduction of commercial TFSAA coating. Further microstructure studies revealed that the improved GC protection of the crystallized PEO coating was realized by suppressing the initiation and propagation of localized pitting due to the improved electrical isolation between the Al-alloy/CFRP interfaces. A high voltage PEO process provides sufficient energy to produce uniform and crystalline ceramic coating consisting of Al2O3 and mullite, which give rise to improved corrosion protection.

Surface Treatment and Bioinspired Coating for 3D-Printed Implants.

Three-dimensional (3D) printing technology has developed rapidly and demonstrates great potential in biomedical applications. Although 3D printing techniques have good control over the macrostructure of metallic implants, the surface properties have superior control over the tissue response. By focusing on the types of surface treatments, the osseointegration activity of the bone-implant interface is enhanced. Therefore, this review paper aims to discuss the surface functionalities of metallic implants regarding their physical structure, chemical composition, and biological reaction through surface treatment and bioactive coating. The perspective on the current challenges and future directions for development of surface treatment on 3D-printed implants is also presented.

Anisotropic Collective Charge Excitations in Quasimetallic 2D Transition-Metal Dichalcogenides.

The quasimetallic 1T' phase 2D transition-metal dichalcogenides (TMDs) consist of 1D zigzag metal chains stacked periodically along a single axis. This gives rise to its prominent physical properties which promises the onset of novel physical phenomena and applications. Here, the in-plane electronic correlations are explored, and new mid-infrared plasmon excitations in 1T' phase monolayer WSe2 and MoS2 are observed using optical spectroscopies. Based on an extensive first-principles study which analyzes the charge dynamics across multiple axes of the atomic-layered systems, the collective charge excitations are found to disperse only along the direction perpendicular to the chains. Further analysis reveals that the interchain long-range coupling is responsible for the coherent 1D charge dynamics and the spin-orbit coupling affects the plasmon frequency. Detailed investigation of these charge collective modes in 2D-chained systems offers opportunities for novel device applications and has implications for the underlying mechanism that governs superconductivity in 2D TMD systems.

Origin of High Thermoelectric Performance in Earth-Abundant Phosphide-Tetrahedrite.

Phosphide-based thermoelectrics are a relatively less studied class of compounds, primarily due to the presence of light elements, which result in high thermal conductivity and inherent stability problems. In this work, we present a stable phosphide-tetrahedrite, Ag6Ge10P12, which possesses the highest zT (∼0.7) among all known phosphides at intermediate temperatures (750 K). We examine the intrinsic electronic and thermal transport properties of this compound by expressing the transport properties in terms of weighted mobility (µW), transport coefficient (σE0), and material quality factor (B), from which we are able to elucidate that the origin of its high zT can be attributed to the platelike Fermi surface and high level of band multiplicity related to its complex band structure. Finally, we discuss the origin of the low lattice thermal conductivity observed in this compound using experimental sound velocity, elastic properties, and Debye-Callaway model, thus laying the foundation for similar stable phosphides as potentially earth-abundant and nontoxic intermediate-temperature thermoelectric materials.

Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphs.

Transition metal oxides exhibit strong structure-property correlations, which has been extensively investigated and utilized for achieving efficient oxygen electrocatalysts. However, high-performance oxide-based electrocatalysts for hydrogen evolution are quite limited, and the mechanism still remains elusive. Here we demonstrate the strong correlations between the electronic structure and hydrogen electrocatalytic activity within a single oxide system Ti2O3. Taking advantage of the epitaxial stabilization, the polymorphism of Ti2O3 is extended by stabilizing bulk-absent polymorphs in the film-form. Electronic reconstructions are realized in the bulk-absent Ti2O3 polymorphs, which are further correlated to their electrocatalytic activity. We identify that smaller charge-transfer energy leads to a substantial enhancement in the electrocatalytic efficiency with stronger hybridization of Ti 3d and O 2p orbitals. Our study highlights the importance of the electronic structures on the hydrogen evolution activity of oxide electrocatalysts, and also provides a strategy to achieve efficient oxide-based hydrogen electrocatalysts by epitaxial stabilization of bulk-absent polymorphs.

Probing the Ionic and Electrochemical Phenomena during Resistive Switching of NiO Thin Films.

Ionic transport and electrochemical reactions underpin the functionality of the memory devices. NiO, as a promising transition metal oxide for developing resistive switching random access memory, has been extensively explored in the terms of the resistive switching. However, there is limited experimental evidence to visualize the ionic processes of the NiO under the external electrical field. In addition, the correlation between the ionic processes and the resistive switching has not been established. To close this gap and also to determine the role of the ionic processes in resistive switching of the NiO, in this study, a series of scanning probe microscopy techniques, including electrochemical strain microscopy (ESM), conductive atomic force microscopy, Kelvin probe force microscopy, and a newly developed first-order reversal curve-IV, are employed to measure the ESM response, the resistive switching performance, the work function, and the ionic dynamics of NiO, respectively. The results in this work have clearly visualized the ionic transport and electrochemical reactions of NiO when subjected to the electrical field. It has been found that the ionic processes and the resistive switching accompanied each other. Furthermore, it is found that the electrochemical reactions play a determinative role in the resistive switching of the NiO, and this electrochemically induced resistive switching performance can be explained by an integrated mechanism that has combined the filamentary and the interfacial effects underlying resistive switching. In addition to providing a better understanding of the resistive switching of NiO, this work also provides effective methods to probe the ionic processes and to correlate these ionic processes to the performance of functional materials.

Probing electrochemically induced resistive switching of TiO2 using SPM techniques.

Resistive switching on the nanoscale is an emerging research field and Scanning Probe Microscopy (SPM) is a powerful tool for studies in this area. Under the SPM tip, the electrical field is very high due to the small tip radius on the order of tens of nanometers, and this can enable a range of ionic/electrochemical phenomena during the resistive switching of the materials under the SPM tip. Although the ionic/electrochemical phenomena have long been considered vital for the resistive switching of materials, a few pieces of experimental evidence, as well as the decoupling of the effects of the electrochemical processes at different stages, are still needed. In this work, we applied SPM based techniques to study resistive switching as well as the electrochemical phenomena during the resistive switching of the TiO2 thin films prepared using Pulse Laser Deposition (PLD). It was found that the reversible or irreversible electrochemical processes initiated at different voltages can promote or degrade the resistive switching behavior of TiO2. Combined with an electrical cell with environmental control, these electrochemical processes have been shown to require the involvement of moisture; the accumulation of oxygen vacancies, protons, and hydroxyls at the tip/TiO2 junction may contribute to the promoting effect of the reversible electrochemical process on resistive switching, while the oxygen vacancy ordering and the injection of protons and hydroxyls into the lattice may lead to the irreversible electrochemical process. This work provides a detailed insight into the characteristics, origins, and the effects of the electrochemical phenomena on resistive switching performance, and will provide a further understanding of the electrochemical phenomena in various functional materials.

Tunable inverted gap in monolayer quasi-metallic MoS2 induced by strong charge-lattice coupling.

Polymorphism of two-dimensional transition metal dichalcogenides such as molybdenum disulfide (MoS2) exhibit fascinating optical and transport properties. Here, we observe a tunable inverted gap (~0.50 eV) and a fundamental gap (~0.10 eV) in quasimetallic monolayer MoS2. Using spectral-weight transfer analysis, we find that the inverted gap is attributed to the strong charge-lattice coupling in two-dimensional transition metal dichalcogenides (2D-TMDs). A comprehensive experimental study, supported by theoretical calculations, is conducted to understand the transition of monolayer MoS2 on gold film from trigonal semiconducting 1H phase to the distorted octahedral quasimetallic 1T' phase. We clarify that electron doping from gold, facilitated by interfacial tensile strain, is the key mechanism leading to its 1H-1T' phase transition, thus resulting in the formation of the inverted gap. Our result shows the importance of charge-lattice coupling to the intrinsic properties of the inverted gap and polymorphism of MoS2, thereby unlocking new possibilities for 2D-TMD-based device fabrication.MoS2 exhibits multiple electronic properties associated with different crystal structures. Here, the authors observe inverted and fundamental gaps through a designed annealing-based strategy, to induce a semiconductor-to-metal phase transition in monolayer-MoS2 on Au, facilitated by interfacial strain and electron transfer from Au to MoS2.

Growth of wafer-scale MoS2 monolayer by magnetron sputtering.

The two-dimensional layer of molybdenum disulfide (MoS2) exhibits promising prospects in the applications of optoelectronics and valleytronics. Herein, we report a successful new process for synthesizing wafer-scale MoS2 atomic layers on diverse substrates via magnetron sputtering. Spectroscopic and microscopic results reveal that these synthesized MoS2 layers are highly homogeneous and crystallized; moreover, uniform monolayers at wafer scale can be achieved. Raman and photoluminescence spectroscopy indicate comparable optical qualities of these as-grown MoS2 with other methods. The transistors composed of the MoS2 film exhibit p-type performance with an on/off current ratio of ∼10(3) and hole mobility of up to ∼12.2 cm(2) V(-1) s(-1). The strategy reported herein paves new ways towards the large scale growth of various two-dimensional semiconductors with the feasibility of controllable doping to realize desired p- or n-type devices.

Near-infrared active metamaterials and their applications in tunable surface-enhanced Raman scattering.

By utilizing the phase change properties of vanadium dioxide (VO2), we have demonstrated the tuning of the electric and magnetic modes of split ring resonators (SRRs) simultaneously within the near IR range. The electric resonance wavelength is blue-shift about 73 nm while the magnetic resonance mode is red-shifted about 126 nm during the phase transition from insulating to metallic phases. Due to the hysteresis phenomenon of VO2 phase transition, both the electric and magnetic modes shifts are hysteretic. In addition to the frequency shift, the magnetic mode has a trend to vanish due to the fact that the metallic phase VO2 has the tendency to short the gap of SRR. We have also demonstrated the application of this active metamaterials in tunable surface-enhanced Raman scattering (SERS), for a fixed excitation laser wavelength, the Raman intensity can be altered significantly by tuning the electric mode frequency of SRR, which is accomplished by controlling the phase of VO2 with an accurate temperature control.

Transparent free-standing metamaterials and their applications in surface-enhanced Raman scattering.

Integration of metamaterials onto a flexible substrate can provide many advantages such as transparency, deformability, light weight and biocompatibility. Here we demonstrate a simple and convenient nickel sacrificial layer-assisted transfer method to fabricate visible-near infrared (IR) metamaterials embedded into a thin polydimethylsiloxane (PDMS) film. Both the structures and the optical properties are maintained after transferring into the PDMS film from a rigid substrate. This PDMS-based metamaterial can behave as a high performance surface enhanced Raman scattering (SERS) device with tunable plasmonic bands, which decouple the preparation of SERS structure and the linkage of targeted molecules to the plasmonic structures. By simply covering the PDMS metamaterials device on the surface with molecules of interest, we demonstrate the application of 2-naphthalenethiol molecules self-assembled on a Au film, highlighting the considerable potential of these PDMS metamaterials as a SERS stamp onto any other substrate. What's more, the PDMS-based nanostructures offer a representative model to investigate the interaction between the plasmonic nanostructure and the substrate consisting of different materials by placing PDMS on the surface of the substrate.

Metamaterials-based label-free nanosensor for conformation and affinity biosensing.

Analysis of molecular interaction and conformational dynamics of biomolecules is of paramount importance in understanding their vital functions in complex biological systems, disease detection, and new drug development. Plasmonic biosensors based upon surface plasmon resonance and localized surface plasmon resonance have become the predominant workhorse for detecting accumulated biomass caused by molecular binding events. However, unlike surface-enhanced Raman spectroscopy (SERS), the plasmonic biosensors indeed are not suitable tools to interrogate vibrational signatures of conformational transitions required for biomolecules to interact. Here, we show that highly tunable plasmonic metamaterials can offer two transducing channels for parallel acquisition of optical transmission and sensitive SERS spectra at the biointerface, simultaneously probing the conformational states and binding affinity of biomolecules, e.g., G-quadruplexes, in different environments. We further demonstrate the use of the metamaterials for fingerprinting and detection of the arginine-glycine-glycine domain of nucleolin, a cancer biomarker that specifically binds to a G-quadruplex, with the picomolar sensitivity.

Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission.

Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO(2) and In(2)O(3) are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications.

Flexible visible-infrared metamaterials and their applications in highly sensitive chemical and biological sensing.

Flexible electronic and photonic devices have been demonstrated in the past decade, with significant promise in low-cost, light-weighted, transparent, biocompatible, and portable devices for a wide range of applications. Herein, we demonstrate a flexible metamaterial (Metaflex)-based photonic device operating in the visible-IR regime, which shows potential applications in high sensitivity strain, biological and chemical sensing. The metamaterial structure, consisting of split ring resonators (SRRs) of 30 nm thick Au or Ag, has been fabricated on poly(ethylene naphthalate) substrates with the least line width of ∼30 nm by electron beam lithography. The absorption resonances can be tuned from middle IR to visible range. The Ag U-shaped SRRs metamaterials exhibit an electric resonance of ∼542 nm and a magnetic resonance of ∼756 nm. Both the electric and magnetic resonance modes show highly sensitive responses to out-of-plane bending strain, surrounding dielectric media, and surface chemical environment. Due to the electric and magnetic field coupling, the magnetic response gives a sensitivity as high as 436 nm/RIU. Our Metaflex devices show superior responses with a shift of magnetic resonance of 4.5 nm/nM for nonspecific bovine serum albumin protein binding and 65 nm for a self-assembled monolayer of 2-naphthalenethiol, respectively, suggesting considerable promise in flexible and transparent photonic devices for chemical and biological sensing.

Vertically aligned cadmium chalcogenide nanowire arrays on muscovite mica: a demonstration of epitaxial growth strategy.

We report a strategy for achieving epitaxial, vertically aligned cadmium chalcogenide (CdS, CdSe, and CdTe) nanowire arrays utilizing van der Waals epitaxy with (001) muscovite mica substrate. The nanowires, grown from a vapor transport process, exhibited diameter uniformity throughout their length, sharp interface to the substrate, and positive correlation between diameter and length with preferential growth direction of [0001] for the monocrystalline wurtzite CdS and CdSe nanowires, but of [111] for zinc blende CdTe nanowires, which also featured abundant twinning boundaries. Self-catalytic vapor-liquid-solid mechanism with hydrogen-assisted thermal evaporation is proposed to intepret the observations. Optical absorption from the as-grown CdSe nanowire arrays on mica at 10 K revealed intense first-order exciton absorption and its longitudinal optical phonon replica. A small Stokes shift (∼1.3 meV) was identified, suggesting the high quality of the nanowires. This study demonstrated the generality of van der Waals epitaxy for the growth of nanowire arrays and their potential applications in optical and energy related devices.

Heteroepitaxial decoration of Ag nanoparticles on Si nanowires: a case study on Raman scattering and mapping.

Metallic nanoparticle-decorated silicon nanowires showed considerable promise in a wide range of applications such as photocatalytic conversion, surface-enhanced Raman scattering, and surface plasmonics. However there is still insufficient amount of Raman scattering in Si nanowires with such decoration. Here we report the heteroepitaxial growth of Ag nanoparticles on Si nanowires by a surface reduction mechanism. The as-grown Ag nanoparticles exhibited highly single crystallinity with a most probable diameter of 25 nm. Raman scattering spectroscopy showed a new sideband feature at 495 cm(-1) below the first order Si transverse optical Raman peak due to HF etching. This new feature sustained after sequential surface treatments and rapid thermal annealing, therefore was attributed to polycrystalline defect at subsurface, which was confirmed by high-resolution transmission electron microscopy observations. Correlated atomic force microscopy and Raman mapping demonstrated that single Ag nanoparticle decoration significantly enhanced Raman signal of Si nanowire by a factor of 7, suggesting that it would be a promising approach to probe phonon confinement and radial breathing mode in individual nanowires down to sub-10 nm regime.

A template and catalyst-free metal-etching-oxidation method to synthesize aligned oxide nanowire arrays: NiO as an example.

Although NiO is one of the canonical functional binary oxides, there has been no report so far on the effective fabrication of aligned single crystalline NiO nanowire arrays. Here we report a novel vapor-based metal-etching-oxidation method to synthesize high-quality NiO nanowire arrays with good vertical alignment and morphology control. In this method, Ni foils are used as both the substrates and the nickel source; NiCl(2) powder serves as the additional Ni source and provides Cl(2) to initiate mild etching. No template is deliberately employed; instead a nanograined NiO scale formed on the NiO foil guides the vapor infiltration and assists the self-assembled growth of NiO nanowires via a novel process comprising simultaneous Cl(2) etching and gentle oxidation. Furthermore, using CoO nanowires and Co-doped NiO as examples, we show that this general method can be employed to produce nanowires of other oxides as well as the doped counterparts.

Shape-controlled fabrication of micro/nanoscale triangle, square, wire-like, and hexagon pits on silicon substrates induced by anisotropic diffusion and silicide sublimation.

We report the fabrication of micro/nanoscale pits with facile shape, orientation, and size controls on an Si surface via an Au-nanoparticles-assisted vapor transport method. The pit dimensions can be continuously tuned from 70 nm to several mum, and the shapes of triangles, squares, and wire/hexagons are prepared on Si (111), (100), and (110) substrates, respectively. This reliable shape control hinges on the anisotropic diffusivity of Co in Si and the sublimation of cobalt silicide nanoislands. The experimental conditions, in particular the substrate orientation and the growth temperature, dictate the pit morphology. On the basis of this understanding of the mechanism and the morphological evolution of the pits, we manage to estimate the diffusion coefficients of Co in bulk Si along the 100 and 111 directions, that is D(100) and D(111). These diffusion coefficients show strong temperature dependence, for example, D(100) is ca. 3 times larger than D(111) at 860 degrees C, while they approach almost the same value at 1000 degrees C. This simple bottom-up route may help to develop new technologies for Si-based nanofabrication and to find potential applications in constructing nanodevices.