Field‐Switchable Broadband Polarizer Based on Reconfigurable Nanowire Assemblies

Reconfigurability is one of the most critical properties of nanophotonic systems and, consequently, methods for enabling a significant degree of functionality are highly sought after. However, dynamically responsive control in top‐down fabricated photonic structures often requires extreme conditions and yields moderate modulation capability. In sharp contrast to top‐down methods, directed self‐assembly of micro‐ and nanoparticles offers a distinct avenue for reconfigurable photonics. In the present work, gold nanowire lattices are formed via electric field directed assembly in order to take advantage of their collective optical properties. The lattices are reconfigured on‐demand between two different functional states, in the form of broadband polarizers. By selectively switching the electric field between two orthogonal electrode pairs, a maximum transmission contrast of ≈50% is observed in the near‐infrared regime. Moreover, the reconfigurable transmission spectra, which are highly dependent on the nanowire size and electric field conditions, are reversible. The demonstrated proof‐of‐concept nanowire lattice polarizer provides potential for electrically reconfigurable photonic devices such as ultra‐compact polarization components, electro‐optic switches, and on‐chip modulators.     

Atomistic Origin of the Enhanced Crystallization Speed and n‐Type Conductivity in Bi‐doped Ge‐Sb‐Te Phase‐Change Materials

Phase‐change alloys are the functional materials at the heart of an emerging digital‐storage technology. The GeTe‐Sb₂Te₃ pseudo‐binary systems, in particular the composition Ge₂Sb₂Te₅ (GST), are one of a handful of materials which meet the unique requirements of a stable amorphous phase, rapid amorphous‐to‐crystalline phase transition, and significant contrasts in optical and electrical properties between material states. The properties of GST can be optimized by doping with p‐block elements, of which Bi has interesting effects on the crystallization kinetics and electrical properties. A comprehensive simulational study of Bi‐doped GST is carried out, looking at trends in behavior and properties as a function of dopant concentration. The results reveal how Bi integrates into the host matrix, and provide insight into its enhancement of the crystallization speed. A straightforward explanation is proposed for the reversal of the charge‐carrier sign beyond a critical doping threshold. The effect of Bi on the optical properties of GST is also investigated. The microscopic insight from this study may assist in the future selection of dopants to optimize the phase‐change properties of GST, and also of other PCMs, and the general methods employed in this work should be applicable to the study of related materials, for example, doped chalcogenide glasses.     

Imprinting of Local Metallic States into VO2 with Ultraviolet Light

Materials exhibiting electronic phase transitions have attracted widespread attention. By switching between metallic and insulating states under external stimuli, the accompanying changes in the electrical and optical properties can be harnessed in novel electronic and optical applications. In this work, a laterally confined conductive pattern is inscribed into an otherwise insulating VO₂ thin film using ultraviolet light, inducing an almost four orders of magnitude decrease in electrical resistivity of the exposed area. The metallic imprint remains in VO₂ after ultraviolet light exposure and can be completely erased by a short low temperature anneal. The ability to optically pattern confined metallic structures provides new opportunities for reconfigurable photonic and plasmonic structures, as well as re‐writable electric circuitry.     

Light‐Controlled Reversible Manipulation of Microgel Particle Size Using Azobenzene‐Containing Surfactant

The light‐induced reversible switching of the swelling of microgel particles triggered by photo‐isomerization and binding/unbinding of a photosensitive azobenzene‐containing surfactant is reported. The interactions between the microgel (N‐isopropylacrylamide, co‐monomer: allyl acetic acid, crosslinker: N,N′‐methylenebisacrylamide) and the surfactant are studied by UV‐Vis spectroscopy, dynamic and electrophoretic light scattering measurements. Addition of the surfactant above a critical concentration leads to contraction/collapse of the microgel. UV light irradiation results in trans‐cis isomerization of the azobenzene unit incorporated into the surfactant tail and causes an unbinding of the more hydrophilic cis isomer from the microgel and its reversible swelling. The reversible contraction can be realized by blue light irradiation that transfers the surfactant back to the more hydrophobic trans conformation, in which it binds to the microgel. The phase diagram of the surfactant‐microgel interaction and transitions (aggregation, contraction, and precipitation) is constructed and allows prediction of changes in the system when the concentration of one or both components is varied. Remote and reversible switching between different states can be realized by either UV or visible light irradiation.     

A Versatile Light‐Switchable Nanorod Memory: Wurtzite ZnO on Perovskite SrTiO3

Integrating materials with distinct lattice symmetries and dimensions is an effective design strategy toward realizing novel devices with unprecedented functionalities, but many challenges remain in synthesis and device design. Here, a heterojunction memory made of wurtzite ZnO nanorods grown on perovskite Nb‐doped SrTiO₃ (NSTO) is reported, the electronic properties of which can be drastically reconfigured by applying a voltage and light. Despite of the distinct lattice structures of ZnO and NSTO, a consistent nature of single crystallinity is achieved in the heterojunctions via the low‐temperature solution‐based hydrothermal growth. In addition to a high and persistent photoconductivity, the ZnO/NSTO heterojunction diode can be turned into a versatile light‐switchable resistive switching memory with highly tunable ON and OFF states. The reversible modification of the effective interfacial energy barrier in the concurrent electronic and ionic processes most likely gives rise to the high susceptibility of the ZnO/NSTO heterojunction to external electric and optical stimuli. Furthermore, this facile synthesis route is promising to be generalized to other novel functional nanodevices integrating materials with diverse structures and properties.     

Nonvolatile Reconfigurable Phase‐Change Metadevices for Beam Steering in the Near Infrared

The development of flat, compact beam‐steering devices with no bulky moving parts is opening up a new route to a variety of exciting applications, such as LIDAR scanning systems for autonomous vehicles, robotics and sensing, free‐space, and even surface wave optical signal coupling. In this paper, the design, fabrication and characterization of innovative, nonvolatile, and reconfigurable beam‐steering metadevices enabled by a combination of optical metasurfaces and chalcogenide phase‐change materials is reported. The metadevices reflect an incident optical beam in a mirror‐like fashion when the phase‐change layer is in the crystalline state, but reflect anomalously at predesigned angles when the phase‐change layer is switched into its amorphous state. Experimental angle‐resolved spectrometry measurements verify that fabricated devices perform as designed, with high efficiencies, up to 40%, when operating at 1550 nm. Laser‐induced crystallization and reamorphization experiments confirm reversible switching of the device. It is believed that reconfigurable phase‐change‐based beam‐steering and beam‐shaping metadevices, such as those reported here, can offer real applications advantages, such as high efficiency, compactness, fast switching times and, due to the nonvolatile nature of chalcogenide phase‐change materials, low power consumption.     

Single Pulse Laser‐Induced Phase Transitions of PLD‐Deposited Ge2Sb2Te5 Films

Phase transformations between amorphous and crystallized states are induced by irradiation with a single nanosecond laser pulse in Ge₂Sb₂Te₅ films grown by pulsed laser deposition. By adjusting the laser fluence, the two different phases are obtained and can be distinguished by their different optical reflectivity. The effect of laser fluence on the crystalline nature of the films is studied in detail. Large structural differences between the laser‐irradiated and thermally annealed films are revealed, due to the high heating rate and short duration of the laser pulse. X‐ray reflectivity measurements show a density increase of 3.58% upon laser‐induced crystallization.     

Photocontrollable Chiral Switching and Selection in Self‐Assembled Plasmonic Nanostructure

Reversible photocontrol of dynamic chirality in self‐assembly systems is of great importance in exploitations of artificial nanomachines for scientific and industrious applications. Here, a new strategy is proposed for achieving optically chiral controls based on photoswitchable plasmonic nanostructures. Chiral plasmonic nanoassemblies that are responsive to optomechanical perturbations exerted by circular polarized light (CPL) in the visible (vis)/near infrared (NIR) region are designed. The reversible photoswitching between opposite chiral states is verified by circular dichroism (CD) spectral signals. Theoretical simulations reveal the key role of optical torques in driving this chiral switching. By regulating light polarization or tuning light frequency to excite different plasmonic modes of the nanostructures, such an optomechanically driven chiral switching can enable a directed mirror‐symmetry breaking and selective chiral amplification in nanoassemblies. This plasmon‐based photoswitching nanosystem can operate at the optical transparent window, showing particular advantages over most of the molecular photoswitches for applications in living systems.     

Finite‐Temperature Properties of Rare‐Earth‐Substituted BiFeO3 Multiferroic Solid Solutions

Rare‐earth substitution in the multiferroic BiFeO₃ (BFO) material holds promise for resolving drawbacks inherent to pure BFO, and for enhancing piezoelectric and magneto‐electric properties via a control of structural and magnetic characteristics. Rare‐earth‐doped BFO solid solutions also exhibit unresolved features, such as the precise nature and atomic characteristics of some intermediate phases. Here, an effective Hamiltonian scheme is developed that allows the investigation of finite‐temperature properties of these systems from an atomistic point of view. In addition to reproducing experimental results of Nd‐doped BFO on structural and magnetic transitions with temperature and composition, this scheme also provides an answer (in form of nanotwins) to these intermediate phases. A striking magneto‐electric effect—namely a paramagnetic–to–antiferromagnetic transition that is induced by an applied electric field—is further predicted near critical compositions, with the resulting structural path being dependent on the orientation of the electric field relative to the antiferroelectric vector.     

Electrochemically Triggered Metal–Insulator Transition between VO2 and V2O5

Distinct properties of multiple phases of vanadium oxide (VO_x) render this material family attractive for advanced electronic devices, catalysis, and energy storage. In this work, phase boundaries of VO_x are crossed and distinct electronic properties are obtained by electrochemically tuning the oxygen content of VO_x thin films under a wide range of temperatures. Reversible phase transitions between two adjacent VO_x phases, VO₂ and V₂O₅, are obtained. Cathodic biases trigger the phase transition from V₂O₅ to VO₂, accompanied by disappearance of the wide band gap. The transformed phase is stable upon removal of the bias while reversible upon reversal of the electrochemical bias. The kinetics of the phase transition is monitored by tracking the time‐dependent response of the X‐ray absorption peaks upon the application of a sinusoidal electrical bias. The electrochemically controllable phase transition between VO₂ and V₂O₅ demonstrates the ability to induce major changes in the electronic properties of VO_x by spanning multiple structural phases. This concept is transferable to other multiphase oxides for electronic, magnetic, or electrochemical applications.     

Nonvolatile Electrical Control and Heterointerface‐Induced Half‐Metallicity of 2D Ferromagnets

Electrical control of atom‐thick van der Waals (vdW) ferromagnets is a key toward future magnetoelectric nanodevices; however, state‐of‐the‐art control approaches are volatile. In this work, introducing ferroelectric switching as an aided layer is demonstrated to be an effective approach toward achieving nonvolatile electrical control of 2D ferromagnets. For example, when a ferromagnetic monolayer CrI₃ and ferroelectric MXene Sc₂CO₂ come together into multiferroic heterostructures, CrI₃ is controlled by polarized states P↑ and P↓ of Sc₂CO₂. P↑ Sc₂CO₂ does not change the semiconducting nature of CrI₃, but surprisingly P↓ Sc₂CO₂ makes CrI₃ half‐metallic. Nonvolatility of the electrical switching between two oppositely ferroelectric polarized states, therefore, indirectly enables nonvolatile electrical control of CrI₃ between ferromagnetic semiconductor and half‐metal. The heterointerface‐induced half‐metallicity in CrI₃ is intrinsic without resorting to any chemical functionalization or external physical modification, which is rather beneficial to the practical application. This work paves the way for nonvolatile electrical control of 2D vdW ferromagnets and applications of CrI₃ in half‐metal‐based nanospintronics.     

Direct and Indirect Exciton Dynamics in Few‐Layered ReS2 Revealed by Photoluminescence and Pump‐Probe Spectroscopy

Atomically thin‐layered ReS₂ with a distorted 1T structure has attracted attention because of its intriguing optical and electronic properties. Here, the direct and indirect exciton dynamics of a three‐layered ReS₂ is investigated by polarization‐resolved transient photoluminescence (PL) and ultrafast pump‐probe spectroscopy. The various time scales of the decay signals of the time‐resolved PL (<10 ps), with monitoring of the populations of electron–hole pairs (exciton), and the transient differential reflectance (≈1 and 100 ps), with monitoring of the populations of electrons and/or holes in the excited states, are observed. These results reveal the characteristic exciton dynamics: rapid relaxation of direct excitons (electron–hole pairs) and slow relaxation of the momentum‐mismatched indirect excitons accompanied by a one‐phonon emission process. These findings provide important information regarding the indirect bandgap nature of few‐layered ReS₂ and its characteristic exciton dynamics, boosting the understanding of the novel electronic and optical properties of atomically thin‐layered ReS₂.     

Organo‐metal Diodes Based on a Nanoparticulate Poly(3,4‐ethylenedioxythiophene) Composite

Diodes composed of a nanoparticulate composite of poly(3,4‐ethylenedioxythiophene) and a Cu–Cu²⁺ redox couple in a poly(ethylene oxide)–LiBF₄ polymer‐electrolyte matrix between Ag and Zr electrodes show rectifications in excess of 50 000 at applied fields of 4 V. These large changes are considered to arise from both rectification at the Zr/ZrO₂ composite interface and from the switching of the composite material between two conductivity states by the application of a low potential field. The preparation and electrochemical characterisation of these novel active devices are discussed.     

Conformational Domain Wall Switch

Domain walls in ferroelectric materials have tantalizing potential in disruptive memory and reconfigurable nanoelectronics technologies. Here, a ferroelectric domain wall switch with three distinct addressable resistance states is demonstrated. The device operation hinges on fully controllable and reversible conformational changes of the domain wall. As validated by atomistic simulations consistent with the experiments, using electric field, the shape—and hence the charge state—of the domain wall and ultimately its conduction are altered. Sequential nanoscale transitions of the walls are visualized directly using stroboscopic‐piezoresponse force microscopy and Kelvin probe microscopy. Anisotropic head‐to‐head domain wall injection, stabilized by the majority carrier type of the ferroelectric, BiFeO₃, is identified as the key factor that enables conformational control.     

Intramolecular Dipole Coupling and Depolarization in Self‐Assembled Monolayers

Quantum mechanical and classical atomistic computational methods are used to simulate the chain‐length dependence of depolarization effects in S(CH₂)_n?1CH₃ and S(CH₂)_n?1COOH self‐assembled monolayers on gold (111) surface. These calculations show that due to weak cooperative effects, the electrostatic properties of alkanethiol monolayers are well described by the gas phase dipole moments of the molecules. However, depolarization in monolayers with the molecules carrying head‐ and tail‐group dipoles, such as COOH‐terminated monolayers, strongly depends on the degree of intramolecular dipole coupling. Thus the electrostatic properties of self‐assembled monolayers can be engineered by changing the length of the aliphatic spacer between the polar groups. The transition from strong to weak coupling regime was found to be accompanied by the change in the sign of the asymptotic value of electrostatic potential above the surface of the monolayers and hence in the sign of the metal work function change. Therefore, the use of weakly polarizable spacers between the polar groups inside the molecules forming the SAM is beneficial for accessing a wider range of work‐function changes.     

Self‐Limited Switching in Ta2O5/TaOx Memristors Exhibiting Uniform Multilevel Changes in Resistance

To facilitate the development of memristive devices, it is essential to resolve the problem of non‐uniformity in switching, which is caused by the random nature of the filamentary switching mechanism in many resistance switching memories based on transition metal oxide. In addition, device parameters such as low‐ and high‐state resistance should be regulated as desired. These issues can be overcome if memristive devices have switching limits for both the low‐ and high‐resistance states and if their resistance values are highly controllable. In this study, a method termed self‐limited switching for uniformly regulating the values of both the low‐ and high‐resistance states is suggested, and the circuit configuration required for the self‐limited switching is established in a Ta₂O₅/TaO_x memristive structure. A method of improving the uniformity of multi‐level resistance states in this memristive system is also proposed.     

Interface‐Engineered Amorphous TiO2‐Based Resistive Memory Devices

Crossbar‐type bipolar resistive memory devices based on low‐temperature amorphous TiO₂ (a‐TiO₂) thin films are very promising devices for flexible nonvolatile memory applications. However, stable bipolar resistive switching from amorphous TiO₂ thin films has only been achieved for Al metal electrodes that can have severe problems like electromigration and breakdown in real applications and can be a limiting factor for novel applications like transparent electronics. Here, amorphous TiO₂‐based resistive random access memory devices are presented that universally work for any configuration of metal electrodes via engineering the top and bottom interface domains. Both by inserting an ultrathin metal layer in the top interface region and by incorporating a thin blocking layer in the bottom interface, more enhanced resistance switching and superior endurance performance can be realized. Using high‐resolution transmission electron microscopy, point energy dispersive spectroscopy, and energy‐filtering transmission electron microscopy, it is demonstrated that the stable bipolar resistive switching in metal/a‐TiO₂/metal RRAM devices is attributed to both interface domains: the top interface domain with mobile oxygen ions and the bottom interface domain for its protection against an electrical breakdown.     

Fragile‐to‐Strong Crossover in Supercooled Liquid Ag‐In‐Sb‐Te Studied by Ultrafast Calorimetry

Phase‐change random‐access memory relies on the reversible crystalline‐glassy phase change in chalcogenide thin films. In this application, the speed of crystallization is critical for device performance: there is a need to combine ultrafast crystallization for switching at high temperature with high resistance to crystallization for non‐volatile data retention near to room temperature. In phase‐change media such as nucleation‐dominated Ge₂Sb₂Te₅, these conflicting requirements are met through the highly “fragile” nature of the temperature dependence of the viscosity of the supercooled liquid. The present study explores, using ultrafast‐heating calorimetry, the equivalent temperature dependence for the growth‐dominated medium Ag‐In‐Sb‐Te. The crystallization shows (unexpectedly) Arrhenius temperature dependence over a wide intermediate temperature range. Here it is shown that this is evidence for a fragile‐to‐strong crossover on cooling the liquid. Such a crossover has many consequences for the interpretation and control of phase‐change kinetics in chalcogenide media, helping to understand the distinction between nucleation‐ and growth‐dominated crystallization, and offering a route to designing improved device performance.     

An Integrated Multifunctional Nanoplatform for Deep‐Tissue Dual‐Mode Imaging

The combination of biocompatible superparamagnetic and photoluminescent nanoparticles (NPs) is intensively studied as highly promising multifunctional (magnetic confinement and targeting, imaging, etc.) tools in biomedical applications. However, most of these hybrid NPs exhibit low signal contrast and shallow tissue penetration for optical imaging due to tissue‐induced optical extinction and autofluorescence, since in many cases, their photoluminescent components emit in the visible spectral range. Yet, the search for multifunctional NPs suitable for high photoluminescence signal‐to‐noise ratio, deep‐tissue imaging is still ongoing. Herein, a biocompatible core/shell/shell sandwich structured Fe₃O₄@SiO₂@NaYF₄:Nd³⁺ nanoplatform possessing excellent superparamagnetic and near‐infrared (excitation) to near‐infrared (emission), i.e., NIR‐to‐NIR photoluminescence properties is developed. They can be rapidly magnetically confined, allowing the NIR photoluminescence signal to be detected through a tissue as thick as 13 mm, accompanied by high T₂ relaxivity in magnetic resonance imaging. The fact that both the excitation and emission wavelengths of these NPs are in the optically transparent biological windows, along with excellent photostability, fast magnetic response, significant T₂‐contrast enhancement, and negligible cytotoxicity, makes them extremely promising for use in high‐resolution, deep‐tissue dual‐mode (optical and magnetic resonance) in vivo imaging and magnetic‐driven applications.     

Strain Engineering of Wave‐like Nanofibers for Dynamically Switchable Adhesive/Repulsive Surfaces

Engineering surfaces that enable the dynamic tuning of their wetting state is critical to many applications including integrated microfluidics systems, flexible electronics, and smart fabrics. Despite extensive progress, most of the switchable surfaces reported are based on ordered structures that suffer from poor scalability and high fabrication costs. Here, a robust and facile bottom‐up approach is demonstrated that allows for the dynamical and reversible switching between lotus leaf (repulsive) and rose petal (adhesive) states by strain engineering of wave‐like nanofiber layers. Interestingly, it is found that the controlled switching between these two distinctive states is sensitive to the shape of the nanofibers. Moreover, it is observed that the structural integrity of the nanofibers is fully preserved during multicycle dynamic switching. The application of these optimal structures is showcased as mechanical hands demonstrating the capture of water microdroplets and their subsequent release in a well‐controlled manner. It is envisioned that this low‐cost and highly scalable surface texture is a powerful platform for the design of portable microfluidics systems, and the fabrication of large‐scale devices for ambient humidity harvesting and water purification.