Polyetherimide (PEI) nanocomposite with WS2 nanotubes.

Nanocomposite materials, integrating nanoscale additives into a polymer matrix, hold immense promise for their exceptional property amalgamation. This study delves into the fabrication and characterization of polyetherimide (PEI) nanocomposite strings fortified with multiwall WS2 nanotubes. The manufacturing process capitalizes on the preferential alignment of WS2 nanotubes along the string axis, corroborated by scanning electron microscopy (SEM). Mechanical measurements unveil a remarkable acceleration of strain hardening in the nanocomposite strings, chiefly attributed to the WS2 nanotubes. Structural analyses via X-ray diffraction (XRD) and wide-angle X-ray scattering (WAXS) reveal intriguing structural alterations during tensile deformation. Notably a semi-crystalline framework ∼100 nm in diameter surrounding the WS2 nanotubes emerges, which is stabilized by the π-π interactions between the PEI chains. The amorphous majority phase (97% by volume) undergoes also major structural changes upon strain becoming more compact and closing-up of the distance beweeetn the PEI chains. Dynamic mechanical analysis (DMA) demonstrates improved thermal stability of the evolved semi-crystalline π-π oriented PEI molecules, characterized by delayed thermal "structural melting", underscoring the pivotal role of the WS2 nanotubes in reinforcing the nanocomposite. The insight gained in this study of WS2 nanotube-reinforced PEI nanocomposite strings, could offer diverse applications for such tailor-made polymeric materials.

High-energy all-solid-state lithium batteries enabled by Co-free LiNiO2 cathodes with robust outside-in structures.

A critical current challenge in the development of all-solid-state lithium batteries (ASSLBs) is reducing the cost of fabrication without compromising the performance. Here we report a sulfide ASSLB based on a high-energy, Co-free LiNiO2 cathode with a robust outside-in structure. This promising cathode is enabled by the high-pressure O2 synthesis and subsequent atomic layer deposition of a unique ultrathin LixAlyZnzOδ protective layer comprising a LixAlyZnzOδ surface coating region and an Al and Zn near-surface doping region. This high-quality artificial interphase enhances the structural stability and interfacial dynamics of the cathode as it mitigates the contact loss and continuous side reactions at the cathode/solid electrolyte interface. As a result, our ASSLBs exhibit a high areal capacity (4.65 mAh cm-2), a high specific cathode capacity (203 mAh g-1), superior cycling stability (92% capacity retention after 200 cycles) and a good rate capability (93 mAh g-1 at 2C). This work also offers mechanistic insights into how to break through the limitation of using expensive cathodes (for example, Co-based) and coatings (for example, Nb-, Ta-, La- or Zr-based) while still achieving a high-energy ASSLB performance.

Unveiling Local Optical Properties Using Nanoimaging Phase Mapping in High-Index Topological Insulator Bi2Se3 Resonant Nanostructures.

Topological insulators are materials characterized by an insulating bulk and high mobility topologically protected surface states, making them promising candidates for future optoelectronic and quantum devices. Although their electronic properties have been extensively studied, their mid-infrared (MIR) properties and prospective photonic capabilities have not been fully uncovered. Here, we use a combination of far-field and near-field nanoscale imaging and spectroscopy to study chemical vapor deposition-grown Bi2Se3 nanobeams (NBs). We extract the MIR optical constants of Bi2Se3, revealing refractive index values as high as n ∼ 6.4, and demonstrate that the NBs support Mie resonances across the MIR. Local near-field reflection phase mapping reveals domains of various phase shifts, providing information on the local optical properties of the NBs. We experimentally measure up to 2π phase-shift across the resonance, in excellent agreement with finite-difference time-domain simulations. This work highlights the potential of Bi2Se3 for quantum circuitry, nonlinear generation, high-Q metaphotonics, and photodetection.

Geometric deep optical sensing.

Geometry, an ancient yet vibrant branch of mathematics, has important and far-reaching impacts on various disciplines such as art, science, and engineering. Here, we introduce an emerging concept dubbed "geometric deep optical sensing" that is based on a number of recent demonstrations in advanced optical sensing and imaging, in which a reconfigurable sensor (or an array thereof) can directly decipher the rich information of an unknown incident light beam, including its intensity, spectrum, polarization, spatial features, and possibly angular momentum. We present the physical, mathematical, and engineering foundations of this concept, with particular emphases on the roles of classical and quantum geometry and deep neural networks. Furthermore, we discuss the new opportunities that this emerging scheme can enable and the challenges associated with future developments.

Optoelectronics of Atomic Metal-Semiconductor Interfaces in Tin-Intercalated MoS2.

Metal-semiconductor interfaces are ubiquitous in modern electronics. These quantum-confined interfaces allow for the formation of atomically thin polarizable metals and feature rich optical and optoelectronic phenomena, including plasmon-induced hot-electron transfer from metal to semiconductors. Here, we report on the metal-semiconductor interface formed during the intercalation of zero-valent atomic layers of tin (Sn) between layers of MoS2, a van der Waals layered material. We demonstrate that Sn interaction leads to the emergence of gap states within the MoS2 band gap and to corresponding plasmonic features between 1 and 2 eV (0.6-1.2 µm). The observed stimulation of the photoconductivity, as well as the extension of the spectral response from the visible regime toward the mid-infrared suggests that hot-carrier generation and internal photoemission take place.

Wafer-Scalable Single-Layer Amorphous Molybdenum Trioxide.

Molybdenum trioxide (MoO3), an important transition metal oxide (TMO), has been extensively investigated over the past few decades due to its potential in existing and emerging technologies, including catalysis, energy and data storage, electrochromic devices, and sensors. Recently, the growing interest in two-dimensional (2D) materials, often rich in interesting properties and functionalities compared to their bulk counterparts, has led to the investigation of 2D MoO3. However, the realization of large-area true 2D (single to few atom layers thick) MoO3 is yet to be achieved. Here, we demonstrate a facile route to obtain wafer-scale monolayer amorphous MoO3 using 2D MoS2 as a starting material, followed by UV-ozone oxidation at a substrate temperature as low as 120 °C. This simple yet effective process yields smooth, continuous, uniform, and stable monolayer oxide with wafer-scale homogeneity, as confirmed by several characterization techniques, including atomic force microscopy, numerous spectroscopy methods, and scanning transmission electron microscopy. Furthermore, using the subnanometer MoO3 as the active layer sandwiched between two metal electrodes, we demonstrate the thinnest oxide-based nonvolatile resistive switching memory with a low voltage operation and a high ON/OFF ratio. These results (potentially extendable to other TMOs) will enable further exploration of subnanometer stoichiometric MoO3, extending the frontiers of ultrathin flexible oxide materials and devices.

Chemical Vapor Deposition of Spherical Amorphous Selenium Mie Resonators for Infrared Meta-Optics.

Applying direct growth and deposition of optical surfaces holds great promise for the advancement of future nanophotonic technologies. Here, we report on a chemical vapor deposition (CVD) technique for depositing amorphous selenium (a-Se) spheres by desorption of selenium from Bi2Se3 and re-adsorption on the substrate. We utilize this process to grow scalable, large area Se spheres on several substrates and characterize their Mie-resonant response in the mid-infrared (MIR) spectral range. We demonstrate size-tunable Mie resonances spanning the 2-16 µm spectral range for single isolated resonators and large area ensembles. We further demonstrate strong absorption dips of up to 90% in ensembles of particles in a broad MIR range. Finally, we show that ultra-high-Q resonances arise in the case where Se Mie-resonators are coupled to low-loss epsilon-near-zero (ENZ) substrates. These findings demonstrate the enabling potential of amorphous Selenium as a versatile and tunable nanophotonic material that may open up avenues for on-chip MIR spectroscopy, chemical sensing, spectral imaging, and large area metasurface fabrication.

Polarization-Driven Asymmetric Electronic Response of Monolayer Graphene to Polymer Zwitterions Probed from Both Sides.

We investigated the nature of graphene surface doping by zwitterionic polymers and the implications of weak in-plane and strong through-plane screening using a novel sample geometry that allows direct access to either the graphene or the polymer side of a graphene/polymer interface. Using both Kelvin probe and electrostatic force microscopies, we observed a significant upshift in the Fermi level in graphene of ∼260 meV that was dominated by a change in polarizability rather than pure charge transfer with the organic overlayer. This physical picture is supported by density functional theory (DFT) calculations, which describe a redistribution of charge in graphene in response to the dipoles of the adsorbed zwitterionic moieties, analogous to a local DC Stark effect. Strong metallic-like screening of the adsorbed dipoles was observed by employing an inverted geometry, an effect identified by DFT to arise from a strongly asymmetric redistribution of charge confined to the side of graphene proximal to the zwitterion dipoles. Transport measurements confirm n-type doping with no significant impact on carrier mobility, thus demonstrating a route to desirable electronic properties in devices that combine graphene with lithographically patterned polymers.

Unveiling the Mechanisms Ruling the Efficient Hydrogen Evolution Reaction with Mitrofanovite Pt3Te4.

By means of electrocatalytic tests, surface-science techniques and density functional theory, we unveil the physicochemical mechanisms ruling the electrocatalytic activity of recently discovered mitrofanovite (Pt3Te4) mineral. Mitrofanovite represents a very promising electrocatalyst candidate for energy-related applications, with a reduction of costs by 47% compared to pure Pt and superior robustness to CO poisoning. We show that Pt3Te4 is a weak topological metal with the Z2 invariant, exhibiting electrical conductivity (∼4 × 106 S/m) comparable with pure Pt. In hydrogen evolution reaction (HER), the electrode based on bulk Pt3Te4 shows a very small overpotential of 46 mV at 10 mA cm-2 and a Tafel slope of 36-49 mV dec-1 associated with the Volmer-Heyrovsky mechanism. The outstanding ambient stability of Pt3Te4 also provides durability of the electrode and long-term stability of its efficient catalytic performances.

Enhancing Light-Matter Interactions in MoS2 by Copper Intercalation.

The intercalation of layered compounds opens up a vast space of new host-guest hybrids, providing new routes for tuning the properties of materials. Here, it is shown that uniform and continuous layers of copper can be intercalated within the van der Waals gap of bulk MoS2 resulting in a unique Cu-MoS2 hybrid. The new Cu-MoS2 hybrid, which remains semiconducting, possesses a unique plasmon resonance at an energy of ≈1eV, giving rise to enhanced optoelectronic activity. Compared with high-performance MoS2 photodetectors, copper-enhanced devices are superior in their spectral response, which extends into the infrared, and also in their total responsivity, which exceeds 104 A W-1 . The Cu-MoS2 hybrids hold promise for supplanting current night-vision technology with compact, advanced multicolor night vision.

Electronic Tuning of Monolayer Graphene with Polymeric "Zwitterists".

Work function engineering of two-dimensional (2D) materials by application of polymer coatings represents a research thrust that promises to enhance the performance of electronic devices. While polymer zwitterions have been demonstrated to significantly modify the work function of both metal electrodes and 2D materials due to their dipole-rich structure, the impact of zwitterion chemical structure on work function modulation is not well understood. To address this knowledge gap, we synthesized a series of sulfobetaine-based zwitterionic random copolymers with variable substituents and used them in lithographic patterning for the preparation of negative-tone resists (i.e., "zwitterists") on monolayer graphene. Ultraviolet photoelectron spectroscopy indicated a significant work function reduction, as high as 1.5 eV, induced by all polymer zwitterions when applied as ultrathin films (<10 nm) on monolayer graphene. Of the polymers studied, the piperidinyl-substituted version, produced the largest dipole normal to the graphene sheet, thereby inducing the maximum work function reduction. Density functional theory calculations probed the influence of zwitterion composition on dipole orientation, while lithographic patterning allowed for evaluation of surface potential contrast via Kelvin probe force microscopy. Overall, this polymer "zwitterist" design holds promise for fine-tuning 2D materials electronics with spatial control based on the chemistry of the polymer coating and the dimensions of the lithographic patterning.

Mutually Reinforced Polymer-Graphene Bilayer Membranes for Energy-Efficient Acoustic Transduction.

Graphene holds promise for thin, ultralightweight, and high-performance nanoelectromechanical transducers. However, graphene-only devices are limited in size due to fatigue and fracture of suspended graphene membranes. Here, a lightweight, flexible, transparent, and conductive bilayer composite of polyetherimide and single-layer graphene is prepared and suspended on the centimeter scale with an unprecedentedly high aspect ratio of 105 . The coupling of the two components leads to mutual reinforcement and creates an ultrastrong membrane that supports 30 000 times its own weight. Upon electromechanical actuation, the membrane pushes a massive amount of air and generates high-quality acoustic sound. The energy efficiency is ≈10-100 times better than state-of-the-art electrodynamic speakers. The bilayer membrane's combined properties of electrical conductivity, mechanical strength, optical transparency, thermal stability, and chemical resistance will promote applications in electronics, mechanics, and optics.

Plasmonics in Atomically Thin Crystalline Silver Films.

Light-matter interaction at the atomic scale rules fundamental phenomena such as photoemission and lasing while enabling basic everyday technologies, including photovoltaics and optical communications. In this context, plasmons, the collective electron oscillations in conducting materials, are important because they allow the manipulation of optical fields at the nanoscale. The advent of graphene and other two-dimensional crystals has pushed plasmons down to genuinely atomic dimensions, displaying appealing properties such as a large electrical tunability. However, plasmons in these materials are either too broad or lying at low frequencies, well below the technologically relevant near-infrared regime. Here, we demonstrate sharp near-infrared plasmons in lithographically patterned wafer-scale atomically thin silver crystalline films. Our measured optical spectra reveal narrow plasmons (quality factor of ∼4), further supported by a low sheet resistance comparable to bulk metal in few-atomic-layer silver films down to seven Ag(111) monolayers. Good crystal quality and plasmon narrowness are obtained despite the addition of a thin passivating dielectric, which renders our samples resilient to ambient conditions. The observation of spectrally sharp and strongly confined plasmons in atomically thin silver holds great potential for electro-optical modulation and optical sensing applications.

Growth Mechanisms and Electronic Properties of Vertically Aligned MoS2.

Thin films of layered semiconductors emerge as highly promising materials for energy harvesting and storage, optoelectronics and catalysis. Their natural propensity to grow as oriented crystals and films is one of their distinct properties under recent focal interest. Specifically, the reaction of transition metal films with chalcogen vapor can result in films of vertically aligned (VA) layers, while metal-oxides react with chalcogens in vapor phase to produce horizontally aligned crystals and films. The growth mechanisms of vertically oriented films are not yet fully understood, as well as their dependence on the initial metal film thickness and growth conditions. Moreover, the resulting electronic properties and the role of defects and disorder had not yet been studied, despite their critical influence on catalytic and device performance. In this work, we study the details of oriented growth of MoS2 with complementary theoretical and experimental approaches. We present a general theoretical model of diffusion-reaction growth that can be applied to a large variety of layered materials synthesized by solid-vapor reaction. Moreover, we inspect the relation of electronic properties to the structure of vertically aligned MoS2 and shed light on the density and character of defects in this material. Our measurements on Si-MoS2 p-n hetero-junction devices point to the existence of polarizable defects that impact applications of vertical transition-metal dichalcogenide materials.

Large-Velocity Saturation in Thin-Film Black Phosphorus Transistors.

A high saturation velocity semiconductor is appealing for applications in electronics and optoelectronics. Thin-film black phosphorus (BP), an emerging layered semiconductor, shows a high carrier mobility and strong mid-infrared photoresponse at room temperature. Here, we report the observation of high intrinsic saturation velocity in 7 to 11 nm thick BP for both electrons and holes as a function of charge-carrier density, temperature, and crystalline direction. We distinguish a drift velocity transition point due to the competition between the electron-impurity and electron-phonon scatterings. We further achieve a room-temperature saturation velocity of 1.2 (1.0) × 107 cm s-1 for hole (electron) carriers at a critical electric field of 14 (13) kV cm-1, indicating an intrinsic current-gain cutoff frequency ∼20 GHz·µm for radio frequency applications. Moreover, the current density is as high as 580 µA µm-1 at a low electric field of 10 kV cm-1. Our studies demonstrate that thin-film BP outperforms silicon in terms of saturation velocity and critical field, revealing its great potential in radio-frequency electronics, high-speed mid-infrared photodetectors, and optical modulators.

Flatlands in the Holy Land: The Evolution of Layered Materials Research in Israel.

The experimental identification of fullerenes in 1985, carbon nanotubes in 1991, inorganic nanotubes in 1992, and graphene in 2004 are cornerstone events that have marked the beginning of the layered nanostructures era of materials science. Nowadays, the synthesis of such low-dimensional systems is a routine practice allowing the controlled fabrication of 0-, 1-, and 2D layered structures of diverse chemical compositions. These systems possess unique physical properties that stem from their structural anisotropy characterized by strong intralayer covalent bonding and weaker interlayer dispersive interactions. This, in turn, results in promising functionality that attracts the attention of scientists from many disciplines including chemists, physicists, material scientists, engineers, as well as life scientists that are interested in both their basic and applied science aspects. Here, a short review of the contribution of the Israeli scientific community to this effort over the past 3 decades, is provided.

Air-Stable Room-Temperature Mid-Infrared Photodetectors Based on hBN/Black Arsenic Phosphorus/hBN Heterostructures.

Layered black phosphorus (BP) has attracted wide attention for mid-infrared photonics and high-speed electronics, due to its moderate band gap and high carrier mobility. However, its intrinsic band gap of around 0.33 electronvolt limits the operational wavelength range of BP photonic devices based on direct interband transitions to around 3.7 µm. In this work, we demonstrate that black arsenic phosphorus alloy (b-As xP1- x) formed by introducing arsenic into BP can significantly extend the operational wavelength range of photonic devices. The as-fabricated b-As0.83P0.17 photodetector sandwiched within hexagonal boron nitride (hBN) shows peak extrinsic responsivity of 190, 16, and 1.2 mA/W at 3.4, 5.0, and 7.7 µm at room temperature, respectively. Moreover, the intrinsic photoconductive effect dominates the photocurrent generation mechanism due to the preservation of pristine properties of b-As0.83P0.17 by complete hBN encapsulation, and these b-As0.83P0.17 photodetectors exhibit negligible transport hysteresis. The broad and large photoresponsivity within mid-infrared resulting from the intrinsic photoconduction, together with the excellent long-term air stability, makes b-As0.83P0.17 alloy a promising alternative material for mid-infrared applications, such as free-space communication, infrared imaging, and biomedical sensing.

Lithographically Patterned Functional Polymer-Graphene Hybrids for Nanoscale Electronics.

Two-dimensional (2D) materials are believed to hold significant promise in nanoscale optoelectronics. While significant progress has been made in this field over the past decade, the ability to control charge carrier density with high spatial precision remains an outstanding challenge in 2D devices. We present an approach that simultaneously addresses the dual issues of charge-carrier doping and spatial precision based on a functional lithographic resist that employs methacrylate polymers containing zwitterionic sulfobetaine pendent groups for noncovalent surface doping of 2D materials. We demonstrate scalable approaches for patterning these polymer films via electron-beam lithography, achieving precise spatial control over carrier doping for fabrication of high-quality, all-2D, lateral p-n junctions in graphene. Our approach preserves all of the desirable structural and electronic properties of graphene while exclusively modifying its surface potential. The functional polymer resist platform and concept offers a facile route toward lithographic doping of graphene- and other 2D material-based optoelectronic devices.

Widely tunable black phosphorus mid-infrared photodetector.

Lately rediscovered orthorhombic black phosphorus (BP) exhibits promising properties for near- and mid-infrared optoelectronics. Although recent electrical measurements indicate that a vertical electric field can effectively reduce its transport bandgap, the impact of the electric field on light-matter interaction remains unclear. Here we show that a vertical electric field can dynamically extend the photoresponse in a 5 nm-thick BP photodetector from 3.7 to beyond 7.7 µm, leveraging the Stark effect. We further demonstrate that such a widely tunable BP photodetector exhibits a peak extrinsic photo-responsivity of 518, 30, and 2.2 mA W-1 at 3.4, 5, and 7.7 µm, respectively, at 77 K. Furthermore, the extracted photo-carrier lifetime indicates a potential operational speed of 1.3 GHz. Our work not only demonstrates the potential of BP as an alternative mid-infrared material with broad optical tunability but also may enable the compact, integrated on-chip high-speed mid-infrared photodetectors, modulators, and spectrometers.

On the impact of Vertical Alignment of MoS2 for Efficient Lithium Storage.

Herein, we report energy storage devices, which are based on densely packed, vertically aligned MoS2 (VA-MoS2) or planar oriented MoS2 (PO-MoS2) and compare their electrochemical performances. The VA-MoS2 films have been processed by chemical vapor deposition (CVD) to reach unprecedented micron-scale thick films while maintaining the vertical alignment for the whole thickness. The VA-MoS2 and the PO-MoS2 films form a high-performance Li-ion electrode, reaching the theoretical limits of reversible capacity for this material (800 mAh/g; twice the specific capacity of graphite). The vertical alignment allows faster charge-discharge rates while maintaining a high specific capacity (C-rate measurements). Noteworthy, the reversible cycling of the Li-ion electrode also benefits from the vertical alignment. In this article, we present the full synthesis, structural and electrochemical characterization of VA-MoS2 along with the properties of PO-MoS2 to deconvolute the intrinsic properties of MoS2 from the influence of the layers' orientation.