Recent advances in process engineering and upcoming applications of metal-organic frameworks.

Progress in metal-organic frameworks (MOFs) has advanced from fundamental chemistry to engineering processes and applications, resulting in new industrial opportunities. The unique features of MOFs, such as their permanent porosity, high surface area, and structural flexibility, continue to draw industrial interest outside the traditional MOF field, both to solve existing challenges and to create new businesses. In this context, diverse research has been directed toward commercializing MOFs, but such studies have been performed according to a variety of individual goals. Therefore, there have been limited opportunities to share the challenges, goals, and findings with most of the MOF field. In this review, we examine the issues and demands for MOF commercialization and investigate recent advances in MOF process engineering and applications. Specifically, we discuss the criteria for MOF commercialization from the views of stability, producibility, regulations, and production cost. This review covers progress in the mass production and formation of MOFs along with future applications that are not currently well known but have high potential for new areas of MOF commercialization.

A 0.2 V Micro-Electromechanical Switch Enabled by a Phase Transition.

Micro-electromechanical (MEM) switches, with advantages such as quasi-zero leakage current, emerge as attractive candidates for overcoming the physical limits of complementary metal-oxide semiconductor (CMOS) devices. To practically integrate MEM switches into CMOS circuits, two major challenges must be addressed: sub 1 V operating voltage to match the voltage levels in current circuit systems and being able to deliver at least millions of operating cycles. However, existing sub 1 V mechanical switches are mostly subject to significant body bias and/or limited lifetimes, thus failing to meet both limitations simultaneously. Here 0.2 V MEM switching devices with ≳106 safe operating cycles in ambient air are reported, which achieve the lowest operating voltage in mechanical switches without body bias reported to date. The ultralow operating voltage is mainly enabled by the abrupt phase transition of nanolayered vanadium dioxide (VO2 ) slightly above room temperature. The phase-transition MEM switches open possibilities for sub 1 V hybrid integrated devices/circuits/systems, as well as ultralow power consumption sensors for Internet of Things applications.

Pressure-Temperature Phase Diagram of Vanadium Dioxide.

The complexity of strongly correlated electron physics in vanadium dioxide is exemplified as its rich phase diagrams of all kinds, which in turn shed light on the mechanisms behind its various phase transitions. In this work, we map out the hydrostatic pressure-temperature phase diagram of vanadium dioxide nanobeams by independently varying pressure and temperature with a diamond anvil cell. In addition to the well-known insulating M1 (monoclinic) and metallic R (tetragonal) phases, the diagram identifies the existence at high pressures of the insulating M1' (monoclinic, more conductive than M1) phase and two metallic phases of X (monoclinic) and O (orthorhombic, at high temperature only). Systematic optical and electrical measurements combined with density functional calculations allow us to delineate their phase boundaries as well as reveal some basic features of the transitions.

Pressurizing Field-Effect Transistors of Few-Layer MoS2 in a Diamond Anvil Cell.

Hydrostatic pressure applied using diamond anvil cells (DAC) has been widely explored to modulate physical properties of materials by tuning their lattice degree of freedom. Independently, electrical field is able to tune the electronic degree of freedom of functional materials via, for example, the field-effect transistor (FET) configuration. Combining these two orthogonal approaches would allow discovery of new physical properties and phases going beyond the known phase space. Such experiments are, however, technically challenging and have not been demonstrated. Herein, we report a feasible strategy to prepare and measure FETs in a DAC by lithographically patterning the nanodevices onto the diamond culet. Multiple-terminal FETs were fabricated in the DAC using few-layer MoS2 and BN as the channel semiconductor and dielectric layer, respectively. It is found that the mobility, conductance, carrier concentration, and contact conductance of MoS2 can all be significantly enhanced with pressure. We expect that the approach could enable unprecedented ways to explore new phases and properties of materials under coupled mechano-electrostatic modulation.

Quantifying van der Waals Interactions in Layered Transition Metal Dichalcogenides from Pressure-Enhanced Valence Band Splitting.

van der Waals (vdW) forces, despite being relatively weak, hold the layers together in transition metal dichalcogenides (TMDs) and play a key role in their band structure evolution, hence profoundly affecting their physical properties. In this work, we experimentally probe the vdW interactions in MoS2 and other TMDs by measuring the valence band maximum (VBM) splitting (Δ) at K point as a function of pressure in a diamond anvil cell. As high pressure increases interlayer wave function coupling, the VBM splitting is enhanced in 2H-stacked MoS2 multilayers but, due to its specific geometry, not in 3R-stacked multilayers, hence allowing the interlayer contribution to be separated out of the total VBM splitting, as well as predicting a negative pressure (2.4 GPa) where the interlayer contribution vanishes. This negative pressure represents the threshold vdW interaction beyond which neighboring layers are electronically decoupled. This approach is compared to first-principles calculations and found to be widely applicable to other group-VI TMDs.

Dynamic Control of Optical Response in Layered Metal Chalcogenide Nanoplates.

Tunable optical transitions in ultrathin layered 2-dimensional (2D) materials unveil the electronic structures of materials and provide exciting prospects for potential applications in optics and photonics. Here, we present our realization of dynamic optical modulation of layered metal chalcogenide nanoplates using ionic liquid (IL) gating over a wide spectral range. The IL gating significantly increased the tuning range of the Fermi level and, as a result, substantially altered the optical transitions in the nanoplates. Using heavily n-doped Bi2Se3 nanoplates, we substantially modulated the light transmission through the ultrathin layer. A tunable, high-transmission spectral window in the visible to near-infrared region has been observed due to simultaneous shifts of both the plasma edge and absorption edge of the material. On the other hand, optical response of multilayer MoSe2 flakes gated by IL has shown enhanced transmission in both positive and negative biases, which is consistent with their ambipolar electrical behavior. The electrically controlled optical property tuning in metal chalcogenide material systems provides new opportunities for potential applications, such as wide spectral range optical modulators, optical filters, and electrically controlled smart windows with extremely low material consumption.

Modulating Photoluminescence of Monolayer Molybdenum Disulfide by Metal-Insulator Phase Transition in Active Substrates.

The atomic thickness and flatness allow properties of 2D semiconductors to be modulated with influence from the substrate. Reversible modulation of these properties requires an "active," reconfigurable substrate, i.e., a substrate with switchable functionalities that interacts strongly with the 2D overlayer. In this work, the photoluminescence (PL) of monolayer molybdenum disulfide (MoS2 ) is modulated by interfacing it with a phase transition material, vanadium dioxide (VO2 ). The MoS2 PL intensity is enhanced by a factor of up to three when the underlying VO2 undergoes the thermally driven phase transition from the insulating to metallic phase. A nonvolatile, reversible way to rewrite the PL pattern is also demonstrated. The enhancement effect is attributed to constructive optical interference when the VO2 turns metallic. This modulation method requires no chemical or mechanical processes, potentially finding applications in new switches and sensors.

Doping against the native propensity of MoS2: degenerate hole doping by cation substitution.

Layered transition metal dichalcogenides (TMDs) draw much attention as the key semiconducting material for two-dimensional electrical, optoelectronic, and spintronic devices. For most of these applications, both n- and p-type materials are needed to form junctions and support bipolar carrier conduction. However, typically only one type of doping is stable for a particular TMD. For example, molybdenum disulfide (MoS2) is natively an n-type presumably due to omnipresent electron-donating sulfur vacancies, and stable/controllable p-type doping has not been achieved. The lack of p-type doping hampers the development of charge-splitting p-n junctions of MoS2, as well as limits carrier conduction to spin-degenerate conduction bands instead of the more interesting, spin-polarized valence bands. Traditionally, extrinsic p-type doping in TMDs has been approached with surface adsorption or intercalation of electron-accepting molecules. However, practically stable doping requires substitution of host atoms with dopants where the doping is secured by covalent bonding. In this work, we demonstrate stable p-type conduction in MoS2 by substitutional niobium (Nb) doping, leading to a degenerate hole density of ∼ 3 × 10(19) cm(-3). Structural and X-ray techniques reveal that the Nb atoms are indeed substitutionally incorporated into MoS2 by replacing the Mo cations in the host lattice. van der Waals p-n homojunctions based on vertically stacked MoS2 layers are fabricated, which enable gate-tunable current rectification. A wide range of microelectronic, optoelectronic, and spintronic devices can be envisioned from the demonstrated substitutional bipolar doping of MoS2. From the miscibility of dopants with the host, it is also expected that the synthesis technique demonstrated here can be generally extended to other TMDs for doping against their native unipolar propensity.

Enhanced Interlayer Charge Injection Efficiency in 2D Multilayer ReS2 via Vertical Double-Side Contacts.

Two-dimensional (2D) van der Waals (vdW) layered materials have provided novel opportunities to explore interesting physical properties such as thickness-dependent bandgap, moiré excitons, superconductivity, and superfluidity. However, the presence of interlayer resistance along the thickness and Schottky barrier in metal-to-2D vdW semiconducting materials causes a limited interlayer charge injection efficiency, perturbing various intrinsic properties of 2D vdW multilayers. Herein, we report a simple but powerful contact electrode design to enhance interlayer carrier injection efficiency along the thickness by constructing vertical double-side contact (VDC) electrodes. A 2-fold extended contact area of VDC not only strongly limits an interlayer resistance contribution to the field-effect mobility and current density at the metal-to-2D semiconductor interface but also significantly suppresses both current transfer length (≤1 µm) and specific contact resistivity (≤1 mΩ·cm2), manifesting clear benefits of VDC in comparison with those in conventional top-contact and bottom-contact configurations. Our layout for contact electrode configuration may suggest an advanced electronic device platform for high-performing 2D optoelectronic devices.

Negative Differential Interlayer Resistance in WSe2 Multilayers via Conducting Channel Migration with Vertical Double-Side Contacts.

The inherent interlayer resistance in two-dimensional (2D) van der Waals (vdW) multilayers is expected to significantly influence the carrier density profile along the thickness, provoking spatial modification and separation of the conducting channel inside the multilayers, in conjunction with the thickness-dependent carrier mobility. However, the effect of the interlayer resistance on the variation in the carrier density profile and its direction along the thickness under different electrostatic bias conditions has been elusive. Here, we reveal the presence of a negative differential interlayer resistance (NDIR) in WSe2 multilayers by considering various contact electrode configurations: (i) bottom contact, (ii) top contact, and (iii) vertical double-side contact (VDC). The contact-structure-dependent shape modification of the transconductance clearly manifests the redistribution of carrier density and indicates the direction of the conducting channel migration along the thickness. Furthermore, the distinct characteristic of the electrically tunable NDIR in 2D WSe2 multilayers is revealed by the observed discrepancy between the top- and bottom-channel resistances determined by four-probe measurements with VDC. Our results provide an optimized device layout and further insights into the distinct carrier transport mechanism in 2D vdW multilayers.

Orientation dependent oxygen exchange kinetics on single crystal SrTiO3 surfaces.

The perovskite SrTiO(3) is arguably one of the most important oxide systems in condensed matter research. In this study, we report measurement of the orientation dependence of oxygen exchange on SrTiO(3) single crystal surfaces by dynamic conductivity measurements under electrochemical perturbations. Activation energy for electrical conduction in the 923-1223 K range at an oxygen partial pressure of ∼10(-11) Pa of (100), (111), and (110) single crystals was found to be 2.6 eV, 2.7 eV, and 3.1 eV, respectively. The equilibration kinetics show profound dependence on the surface orientation and are modelled using a heterogeneous relaxation process. All surfaces show similar cationic sub-lattice limited rate behavior with (111), (100), and (110) having the fastest, intermediate, and slowest rates, respectively. We discuss the orientation dependence and its relation to local atomic structure in light of previous experimental and theoretical studies.

Tailorable Electronic and Electric Properties of Graphene with Selective Decoration of Silver Nanoparticles by Laser-Assisted Photoreduction.

While graphene shows great potential for diverse device applications, to broaden the scope of graphene-based device applications further, it would be necessary to tune the electronic state of graphene and its resultant electrical properties properly. Surface decoration with metal nanoparticles is one of the efficient doping methods to control the properties of two-dimensional materials. Here, we report the p-type doping effects in single-layer graphene decorated with silver nanoparticles (AgNPs) that were formed area-selectively by the facile one-step photoreduction (PR) process based on focused-laser irradiation. During the PR process, AgNPs were reduced on graphene in AgNO3 solution by laser-driven photoexcitation followed by chemical reactions. Based on scanning electron microscopy analyses, the morphology characteristics of AgNPs were shown to be modulated by the laser dwell time and power controllably. Further, p-type doping effects were demonstrated using graphene-field-effect transistor structures whose graphene channels were selectively decorated with AgNPs by the PR process, as validated by the decrease in channel resistance and the shift of the Dirac point voltage. Moreover, the growth of AgNPs was observed to be more active on the graphene channel that was laser-annealed ahead of the PR process, leading to enhancing the efficiency of this approach for altering device characteristics.

Nanoscale mapping of temperature-dependent conduction in an epitaxial VO2 film grown on an Al2O3 substrate.

Vanadium dioxide (VO2) is one of the extensively studied strongly correlated oxides due to its intriguing insulator-metal transition near room temperature. In this work, we investigated temperature-dependent nanoscale conduction in an epitaxial VO2 film grown on an Al2O3 substrate using conductive-atomic force microscopy (C-AFM). We observed that only the regions near the grain boundaries are conductive, producing intriguing donut patterns in C-AFM images. Such donut patterns were observed in the entire measured temperature range (300-355 K). The current values near the grain boundaries increased by approximately two orders of magnitude with an increase in the temperature, which is consistent with the macroscopic transport data. The spatially-varied conduction behavior is ascribed to the coexistence of different monoclinic phases, i.e., M1 and M2 phases, based on the results of temperature-dependent Raman spectroscopy. Furthermore, we investigated the conduction mechanism in the relatively conductive M1 phase regions at room temperature using current-voltage (I-V) spectroscopy and deep data analysis. Bayesian linear unmixing and k-means clustering showed three distinct types of conduction behavior, which classical C-AFM cannot resolve. We found that the conduction in the M1 phase regions can be explained by the Poole-Frenkel mechanism. This work provides deep insight into IMT behavior in the epitaxial VO2 thin film at the nanoscale, especially the coexistence and evolution of the M1 and M2 phases. This work also highlights that I-V spectroscopy combined with deep data analysis is very powerful in investigating local transport in complex oxides and various material systems.

Terahertz spectroscopy studies on epitaxial vanadium dioxide thin films across the metal-insulator transition.

We present results on terahertz (THz) spectroscopy on epitaxial vanadium dioxide (VO(2)) films grown on sapphire across the metal-insulator transition. X-ray diffraction indicates the VO(2) film is highly oriented with the crystallographic relationship: (002)(film)//(0006)(sub) and [010](film)//[2 ̅1 ̅10](sub). THz studies measuring the change in transmission as a function of temperature demonstrate an 85% reduction in transmission as the thin film completes its phase transition to the conducting phase, which is much greater than the previous observation on polycrystalline films. This indicates the crucial role of microstructure and phase homogeneity in influencing THz properties.

Studies on oxygen chemical surface exchange and electrical conduction in thin film nanostructured titania at high temperatures and varying oxygen pressure.

We report on oxygen surface exchange studies in ∼450-nm-thick nanocrystalline titania films with an average grain size of ∼13 nm by electrical conductivity relaxation along with the conductivity measurements at varying temperatures and oxygen partial pressures (pO(2)s). By electrochemical impedance spectroscopy technique, the high temperature conductivity was measured in the pO(2) range from ∼10(-16) to ∼10(-6) Pa at temperatures from 973 to 1223 K and activation energy, ΔE(a), for conduction was estimated as ∼3.23 eV at pO(2) ∼10(-11) Pa. Under reducing atmosphere (pO(2) < 10(-6) Pa), two distinct n-type conduction regimes were observed and corresponding predominant defects are discussed while, at high pO(2) regime (pO(2) >10(-6) Pa), ionic conduction appears dominant leading to a conductivity plateau. The surface relaxation was observed to have two independent time constants likely originating from microstructural effects. The surface exchange coefficients are measured as ∼10(-8)-10(-7) m∕s and ∼10(-9)-10(-8) m∕s for each contribution with ΔE(a)s of 2.79 and 1.82 eV, respectively, without much pO(2) dependence across several orders of pO(2) range of ∼10(-16)-10(-6) Pa in the temperature range between 973 and 1223 K. The results are of potential relevance to understanding the near-surface chemical phenomena in nanocrystalline titania which is of great interest for energy and environmental studies.

In-Situ Nano-Auger Probe of Chloride-Ions during CH3NH3PbI3-xClx Perovskite Formation.

Organo-halide perovskite solar cells (PSCs) have emerged as next-generation photovoltaics, owing to their high power-conversion efficiency (PCE), lower production cost, and high flexibility. ABX3-structured methylammonium lead triiodide (CH3NH3PbI3 or MAPbI3) perovskite is a widely studied light-absorbing material in PSCs. Interestingly, a small amount of chlorine incorporation into MAPbI3 increases charge carrier diffusion lengths (from 129 nm to 1069 nm), which enables planar structured PSCs with high PCEs. However, existence of chloride ions in the final perovskite film is still under debate. Contrastingly, few studies reported a negligible amount or absence of chloride ions in the final film, while others reported detection of chloride ions in the final film. Herein, we observed the microstructure and chlorine content of MAPbI3-xClx thin films with increasing temperature via an in-situ nano-Auger spectroscopy and in-situ scanning electron microscopic analysis. The relative precipitation of MAPbI3-xClx films occur at lower temperature and MAPbI3-xClx grains grow faster than those of MAPbI3 grains. Local concentrations of chlorine at intragrain and the vicinity of grain boundary were analyzed to understand the behavior and role of the chloride ions during the microstructural evolution of the MAPbI3-xClx films.

Electric-field control of spin dynamics during magnetic phase transitions.

Controlling magnetization dynamics is imperative for developing ultrafast spintronics and tunable microwave devices. However, the previous research has demonstrated limited electric-field modulation of the effective magnetic damping, a parameter that governs the magnetization dynamics. Here, we propose an approach to manipulate the damping by using the large damping enhancement induced by the two-magnon scattering and a nonlocal spin relaxation process in which spin currents are resonantly transported from antiferromagnetic domains to ferromagnetic matrix in a mixed-phased metallic alloy FeRh. This damping enhancement in FeRh is sensitive to its fraction of antiferromagnetic and ferromagnetic phases, which can be dynamically tuned by electric fields through a strain-mediated magnetoelectric coupling. In a heterostructure of FeRh and piezoelectric PMN-PT, we demonstrated a more than 120% modulation of the effective damping by electric fields during the antiferromagnetic-to-ferromagnetic phase transition. Our results demonstrate an efficient approach to controlling the magnetization dynamics, thus enabling low-power tunable electronics.

Reconfigurable Local Photoluminescence of Atomically-Thin Semiconductors via Ferroelectric-Assisted Effects.

Combining a pair of materials of different structural dimensions and functional properties into a hybrid material system may realize unprecedented multi-functional device applications. Especially, two-dimensional (2D) materials are suitable for being incorporated into the heterostructures due to their colossal area-to-volume ratio, excellent flexibility, and high sensitivity to interfacial and surface interactions. Semiconducting molybdenum disulfide (MoS2), one of the well-studied layered materials, has a direct band gap as one molecular layer and hence, is expected to be one of the promising key materials for next-generation optoelectronics. Here, using lateral 2D/3D heterostructures composed of MoS2 monolayers and nanoscale inorganic ferroelectric thin films, reversibly tunable photoluminescence has been demonstrated at the microscale to be over 200% upon ferroelectric polarization reversal by using nanoscale conductive atomic force microscopy tips. Also, significant ferroelectric-assisted modulation in electrical properties has been achieved from field-effect transistor devices based on the 2D/3D heterostructrues. Moreover, it was also shown that the MoS2 monolayer can be an effective electric field barrier in spite of its sub-nanometer thickness. These results would be of close relevance to exploring novel applications in the fields of optoelectronics and sensor technology.

Black Arsenic: A Layered Semiconductor with Extreme In-Plane Anisotropy.

2D layered materials have emerged in recent years as a new platform to host novel electronic, optical, or excitonic physics and develop unprecedented nanoelectronic and energy applications. By definition, these materials are strongly anisotropic between the basal plane and cross the plane. The structural and property anisotropies inside their basal plane, however, are much less investigated. Black phosphorus, for example, is a 2D material that has such in-plane anisotropy. Here, a rare chemical form of arsenic, called black-arsenic (b-As), is reported as a cousin of black phosphorus, as an extremely anisotropic layered semiconductor. Systematic characterization of the structural, electronic, thermal, and electrical properties of b-As single crystals is performed, with particular focus on its anisotropies along two in-plane principle axes, armchair (AC) and zigzag (ZZ). The analysis shows that b-As exhibits higher or comparable electronic, thermal, and electric transport anisotropies between the AC and ZZ directions than any other known 2D crystals. Such extreme in-plane anisotropies can potentially implement novel ideas for scientific research and device applications.

Environmental stability of 2D anisotropic tellurium containing nanomaterials: anisotropic to isotropic transition.

We report on the vibrational (Raman) spectrum and structural transformation of semiconducting pseudo-1D GaTe and ZrTe3 nanomaterials driven by ambient molecular interactions at the nanoscale by angle-resolved Raman spectroscopy, atomic force microscopy (AFM), and environmental X-ray photoelectron (XPS) measurements. The results show that tellurium containing pseudo-1D materials undergo drastic structural and physical changes within a week. During this process, new Raman peaks start to emerge and surface roughness increases substantially. Surprisingly, aged Raman spectra of GaTe, ZrTe3, and α-TeOx show striking similarities suggesting that oxidation of tellurium takes place. Careful, environmental tests reveal that the interaction between GaTe and H2O molecules forms Te-O bonds at the outermost layers of GaTe which leads to newly emerging Raman peaks, a much reduced Schottky junction current density, and an anisotropic to isotropic structural transition. These findings offer fresh interpretation of the aging mechanisms for these material systems, provide new interpretation of the Raman spectrum of aged GaTe which was previously presumed to be of the hexagonal phase, and introduce an anisotropic to isotropic transformation effect induced by molecular interactions on the surface.