Substrate Engineering for Chemical Vapor Deposition Growth of Large-Scale 2D Transition Metal Dichalcogenides.

The large-scale production of 2D transition metal dichalcogenides (TMDs) is essential to realize their industrial applications. Chemical vapor deposition (CVD) has been considered as a promising method for the controlled growth of high-quality and large-scale 2D TMDs. During a CVD process, the substrate plays a crucial role in anchoring the source materials, promoting the nucleation and stimulating the epitaxial growth. It thus significantly affects the thickness, microstructure, and crystal quality of the products, which are particularly important for obtaining 2D TMDs with expected morphology and size. Here, an insightful review is provided by focusing on the recent development associated with the substrate engineering strategies for CVD preparation of large-scale 2D TMDs. First, the interaction between 2D TMDs and substrates, a key factor for the growth of high-quality materials, is systematically discussed by combining the latest theoretical calculations. Based on this, the effect of various substrate engineering approaches on the growth of large-area 2D TMDs is summarized in detail. Finally, the opportunities and challenges of substrate engineering for the future development of 2D TMDs are discussed. This review might provide deep insight into the controllable growth of high-quality 2D TMDs toward their industrial-scale practical applications.

Recent Development of Halide Perovskite Materials and Devices for Ionizing Radiation Detection.

Ionizing radiation such as X-rays and γ-rays has been extensively studied and used in various fields such as medical imaging, radiographic nondestructive testing, nuclear defense, homeland security, and scientific research. Therefore, the detection of such high-energy radiation with high-sensitivity and low-cost-based materials and devices is highly important and desirable. Halide perovskites have emerged as promising candidates for radiation detection due to the large light absorption coefficient, large resistivity, low leakage current, high mobility, and simplicity in synthesis and processing as compared with commercial silicon (Si) and amorphous selenium (a-Se). In this review, we provide an extensive overview of current progress in terms of materials development and corresponding device architectures for radiation detection. We discuss the properties of a plethora of reported compounds involving organic-inorganic hybrid, all-inorganic, all-organic perovskite and antiperovskite structures, as well as the continuous breakthroughs in device architectures, performance, and environmental stability. We focus on the critical advancements of the field in the past few years and we provide valuable insight for the development of next-generation materials and devices for radiation detection and imaging applications.

Developing a Chemical and Structural Understanding of the Surface Oxide in a Niobium Superconducting Qubit.

Superconducting thin films of niobium have been extensively employed in transmon qubit architectures. Although these architectures have demonstrated improvements in recent years, further improvements in performance through materials engineering will aid in large-scale deployment. Here, we use information retrieved from secondary ion mass spectrometry and electron microscopy to conduct a detailed assessment of the surface oxide that forms in ambient conditions for transmon test qubit devices patterned from a niobium film. We observe that this oxide exhibits a varying stoichiometry with NbO and NbO2 found closer to the niobium film/oxide interface and Nb2O5 found closer to the surface. In terms of structural analysis, we find that the Nb2O5 region is semicrystalline in nature and exhibits randomly oriented grains on the order of 1-3 nm corresponding to monoclinic N-Nb2O5 that are dispersed throughout an amorphous matrix. Using fluctuation electron microscopy, we are able to map the relative crystallinity in the Nb2O5 region with nanometer spatial resolution. Through this correlative method, we observe that the highly disordered regions are more likely to contain oxygen vacancies and exhibit weaker bonds between the niobium and oxygen atoms. Based on these findings, we expect that oxygen vacancies likely serve as a decoherence mechanism in quantum systems.

Direct Patterning of Optoelectronic Nanostructures Using Encapsulated Layered Transition Metal Dichalcogenides.

Direct top-down nanopatterning of semiconductors is a powerful tool for engineering properties of optoelectronic devices. Translating this approach to two-dimensional semiconductors such as monolayer transition metal dichalcogenides (TMDs) is challenging because of both the small scales required for confinement and the degradation of electronic and optical properties caused by high-energy and high-dose electron radiation used for high-resolution top-down direct electron beam patterning. We show that encapsulating a TMD monolayer with hexagonal boron nitride preserves the narrow exciton linewidths and emission intensity typical in such heterostructures after electron beam lithography, allowing direct patterning of functional optical monolayer nanostructures on scales of a few tens of nanometers. We leverage this fabrication method to study size-dependent effects on nanodot arrays of MoS2 and MoSe2 as well as laterally confined electrical transport devices, demonstrating the potential of top-down lithography for nanoscale TMD optoelectronics.

Mechanistic Investigation of Molybdenum Disulfide Defect Photoluminescence Quenching by Adsorbed Metallophthalocyanines.

Lattice defects play an important role in determining the optical and electrical properties of monolayer semiconductors such as MoS2. Although the structures of various defects in monolayer MoS2 are well studied, little is known about the nature of the fluorescent defect species and their interaction with molecular adsorbates. In this study, the quenching of the low-temperature defect photoluminescence (PL) in MoS2 is investigated following the deposition of metallophthalocyanines (MPcs). The quenching is found to significantly depend on the identity of the phthalocyanine metal, with the quenching efficiency decreasing in the order CoPc > CuPc > ZnPc, and almost no quenching by metal-free H2Pc is observed. Time-correlated single photon counting (TCSPC) measurements corroborate the observed trend, indicating a decrease in the defect PL lifetime upon MPc adsorption, and the gate voltage-dependent PL reveals the suppression of the defect emission even at large Fermi level shifts. Density functional theory modeling argues that the MPc complexes stabilize dark negatively charged defects over luminescent neutral defects through an electrostatic local gating effect. These results demonstrate the control of defect-based excited-state decay pathways via molecular electronic structure tuning, which has broad implications for the design of mixed-dimensional optoelectronic devices.

Tuning of Optical Phonons in α-MoO3-VO2 Multilayers.

Merging the properties of VO2 and van der Waals (vdW) materials has given rise to novel tunable photonic devices. Despite recent studies on the effect of the phase change of VO2 on tuning near-field optical response of phonon polaritons in the infrared range, active tuning of optical phonons (OPhs) using far-field techniques has been scarce. Here, we investigate the tunability of OPhs of α-MoO3 in a multilayer structure with VO2. Our experiments show the frequency and intensity tuning of 2 cm-1 and 11% for OPhs in the [100] direction and 2 cm-1 and 28% for OPhs in the [010] crystal direction of α-MoO3. Using the effective medium theory and dielectric models of each layer, we verify these findings with simulations. We then use loss tangent analysis and remove the effect of the substrate to understand the origin of these spectral characteristics. We expect that these findings will assist in intelligently designing tunable photonic devices for infrared applications, such as tunable camouflage and radiative cooling devices.

Spatial Mapping of Electrostatic Fields in 2D Heterostructures.

In situ electron microscopy is an effective tool for understanding the mechanisms driving novel phenomena in 2D structures. However, due to practical challenges, it is difficult to address these technologically relevant 2D heterostructures with electron microscopy. Here, we use the differential phase contrast (DPC) imaging technique to build a methodology for probing local electrostatic fields during electrical operation with nanoscale spatial resolution in such materials. We find that, by combining a traditional DPC setup with a high-pass filter, we can largely eliminate electric fluctuations emanating from short-range atomic potentials. Using a method based on this filtering algorithm, a priori electric field expectations can be directly compared with experimentally derived values to readily identify inhomogeneities and potentially problematic regions. We use this platform to analyze the electric field and charge density distribution across layers of hBN and MoS2.

Valley-selective optical Stark effect of exciton-polaritons in a monolayer semiconductor.

Selective breaking of degenerate energy levels is a well-known tool for coherent manipulation of spin states. Though most simply achieved with magnetic fields, polarization-sensitive optical methods provide high-speed alternatives. Exploiting the optical selection rules of transition metal dichalcogenide monolayers, the optical Stark effect allows for ultrafast manipulation of valley-coherent excitons. Compared to excitons in these materials, microcavity exciton-polaritons offer a promising alternative for valley manipulation, with longer lifetimes, enhanced valley coherence, and operation across wider temperature ranges. Here, we show valley-selective control of polariton energies in WS2 using the optical Stark effect, extending coherent valley manipulation to the hybrid light-matter regime. Ultrafast pump-probe measurements reveal polariton spectra with strong polarization contrast originating from valley-selective energy shifts. This demonstration of valley degeneracy breaking at picosecond timescales establishes a method for coherent control of valley phenomena in exciton-polaritons.

Correction: Topology of transition metal dichalcogenides: the case of the core-shell architecture.

Correction for 'Topology of transition metal dichalcogenides: the case of the core-shell architecture' by Jennifer G. DiStefano et al., Nanoscale, 2020, 12, 23897-23919, DOI: 10.1039/D0NR06660E.

Making the Most of your Electrons: Challenges and Opportunities in Characterizing Hybrid Interfaces with STEM.

Inspired by the unique architectures composed of hard and soft materials in natural and biological systems, synthetic hybrid structures and associated soft-hard interfaces have recently evoked significant interest. Soft matter is typically dominated by fluctuations even at room temperature, while hard matter (which often serves as the substrate or anchor for the soft component) is governed by rigid mechanical behavior. This dichotomy offers considerable opportunities to leverage the disparate properties offered by these components across a wide spectrum spanning from basic science to engineering insights with significant technological overtones. Such hybrid structures, which include polymer nanocomposites, DNA functionalized nanoparticle superlattices and metal organic frameworks to name a few, have delivered promising insights into the areas of catalysis, environmental remediation, optoelectronics, medicine, and beyond. The interfacial structure between these hard and soft phases exists across a variety of length scales and often strongly influence the functionality of hybrid systems. While scanning/transmission electron microscopy (S/TEM) has proven to be a valuable tool for acquiring intricate molecular and nanoscale details of these interfaces, the unusual nature of hybrid composites presents a suite of challenges that make assessing or establishing the classical structure-property relationships especially difficult. These include challenges associated with preparing electron-transparent samples and obtaining sufficient contrast to resolve the interface between dissimilar materials given the dose sensitivity of soft materials. We discuss each of these challenges and supplement a review of recent developments in the field with additional experimental investigations and simulations to present solutions for attaining a nano or atomic-level understanding of these interfaces. These solutions present a host of opportunities for investigating and understanding the role interfaces play in this unique class of functional materials.

Topology of transition metal dichalcogenides: the case of the core-shell architecture.

Non-planar architectures of the traditionally flat 2D materials are emerging as an intriguing paradigm to realize nascent properties within the family of transition metal dichalcogenides (TMDs). These non-planar forms encompass a diversity of curvatures, morphologies, and overall 3D architectures that exhibit unusual characteristics across the hierarchy of length-scales. Topology offers an integrated and unified approach to describe, harness, and eventually tailor non-planar architectures through both local and higher order geometry. Topological design of layered materials intrinsically invokes elements highly relevant to property manipulation in TMDs, such as the origin of strain and its accommodation by defects and interfaces, which have broad implications for improved material design. In this review, we discuss the importance and impact of geometry on the structure and properties of TMDs. We present a generalized geometric framework to classify and relate the diversity of possible non-planar TMD forms. We then examine the nature of curvature in the emerging core-shell architecture, which has attracted high interest due to its versatility and design potential. We consider the local structure of curved TMDs, including defect formation, strain, and crystal growth dynamics, and factors affecting the morphology of core-shell structures, such as synthesis conditions and substrate morphology. We conclude by discussing unique aspects of TMD architectures that can be leveraged to engineer targeted, exotic properties and detail how advanced characterization tools enable detection of these features. Varying the topology of nanomaterials has long served as a potent methodology to engineer unusual and exotic properties, and the time is ripe to apply topological design principles to TMDs to drive future nanotechnology innovation.

Lithography-free IR polarization converters via orthogonal in-plane phonons in α-MoO3 flakes.

Exploiting polaritons in natural vdW materials has been successful in achieving extreme light confinement and low-loss optical devices and enabling simplified device integration. Recently, α-MoO3 has been reported as a semiconducting biaxial vdW material capable of sustaining naturally orthogonal in-plane phonon polariton modes in IR. In this study, we investigate the polarization-dependent optical characteristics of cavities formed using α-MoO3 to extend the degrees of freedom in the design of IR photonic components exploiting the in-plane anisotropy of this material. Polarization-dependent absorption over 80% in a multilayer Fabry-Perot structure with α-MoO3 is reported without the need for nanoscale fabrication on the α-MoO3. We observe coupling between the α-MoO3 optical phonons and the Fabry-Perot cavity resonances. Using cross-polarized reflectance spectroscopy we show that the strong birefringence results in 15% of the total power converted into the orthogonal polarization with respect to incident wave. These findings can open new avenues in the quest for polarization filters and low-loss, integrated planar IR photonics and in dictating polarization control.

Direct Visualization of Electric-Field-Induced Structural Dynamics in Monolayer Transition Metal Dichalcogenides.

Layered transition metal dichalcogenides offer many attractive features for next-generation low-dimensional device geometries. Due to the practical and fabrication challenges related to in situ methods, the atomistic dynamics that give rise to realizable macroscopic device properties are often unclear. In this study, in situ transmission electron microscopy techniques are utilized in order to understand the structural dynamics at play, especially at interfaces and defects, in the prototypical film of monolayer MoS2 under electrical bias. Through our sample fabrication process, we clearly identify the presence of mass transport in the presence of a lateral electric field. In particular, we observe that the voids present at grain boundaries combine to induce structural deformation. The electric field mediates a net vacancy flux from the grain boundary interior to the exposed surface edge sites that leaves molybdenum clusters in its wake. Following the initial biasing cycles, however, the mass flow is largely diminished and the resultant structure remains stable over repeated biasing. We believe insights from this work can help explain observations of nonuniform heating and preferential oxidation at grain boundary sites in these materials.

S-Palmitoylation of junctophilin-2 is critical for its role in tethering the sarcoplasmic reticulum to the plasma membrane.

Junctophilins (JPH1-JPH4) are expressed in excitable and nonexcitable cells, where they tether endoplasmic/sarcoplasmic reticulum (ER/SR) and plasma membranes (PM). These ER/SR-PM junctions bring Ca-release channels in the ER/SR and Ca as well as Ca-activated K channels in the PM to within 10-25 nm. Such proximity is critical for excitation-contraction coupling in muscles, Ca modulation of excitability in neurons, and Ca homeostasis in nonexcitable cells. JPHs are anchored in the ER/SR through the C-terminal transmembrane domain (TMD). Their N-terminal Membrane-Occupation-Recognition-Nexus (MORN) motifs can bind phospholipids. Whether MORN motifs alone are sufficient to stabilize JPH-PM binding is not clear. We investigate whether S-palmitoylation of cysteine (Cys), a critical mechanism controlling peripheral protein binding to PM, occurs in JPHs. We focus on JPH2 that has four Cys residues: three flanking the MORN motifs and one in the TMD. Using palmitate-alkyne labeling, Cu(I)-catalyzed alkyne-azide cycloaddition reaction with azide-conjugated biotin, immunoblotting, proximity-ligation-amplification, and various imaging techniques, we show that JPH2 is S-palmitoylatable, and palmitoylation is essential for its ER/SR-PM tether function. Palmitoylated JPH2 binds to lipid-raft domains in PM, whereas palmitoylation of TMD-located Cys stabilizes JPH2's anchor in the ER/SR membrane. Binding to lipid-raft domains protects JPH2 from depalmitoylation. Unpalmitoylated JPH2 is largely excluded from lipid rafts and loses the ability to form stable ER/SR-PM junctions. In adult ventricular myocytes, native JPH2 is S-palmitoylatable, and palmitoylated JPH2 forms distinct PM puncta. Sequence alignment reveals that the palmitoylatable Cys residues in JPH2 are conserved in other JPHs, suggesting that palmitoylation may also enhance ER/SR-PM tethering by these proteins.

Dynamic palmitoylation regulates trafficking of K channel interacting protein 2 (KChIP2) across multiple subcellular compartments in cardiac myocytes.

BACKGROUND: K channel interacting protein 2 (KChIP2), initially cloned as Kv4 channel modulator, is a multi-tasking protein. In addition to modulating several cardiac ion channels at the plasma membrane, it can also modulate microRNA transcription inside nuclei, and interact with presenilins to modulate Ca release through RyR2 in the cytoplasm. However, the mechanism regulating its subcellular distribution is not clear. OBJECTIVE: We tested whether palmitoylation drives KChIP2 trafficking and distribution in cells, and whether the distribution pattern of KChIP2 in cardiac myocytes is sensitive to cellular milieu. METHOD: We conducted imaging and biochemical experiments on palmitoylatable and unpalmitoylatable KChIP2 variants expressed in COS-7 cells and in cardiomyocytes, and on native KChIP2 in myocytes. RESULTS: In COS-7 cells, palmitoylatable KChIP2 clustered to plasma membrane, while unpalmitoylatable KChIP2 exhibited higher cytoplasmic mobility and faster nuclear entry. The same differences in distribution and mobility were observed when these KChIP2 variants were expressed in cardiac myocytes, indicating that the palmitoylation-dependent distribution and trafficking are intrinsic properties of KChIP2. Importantly, acute stress in a rat model of cardiac arrest/resuscitation induced changes in native KChIP2 resembling those of KChIP2 depalmitoylation, promoting KChIP2 nuclear entry. CONCLUSION: The palmitoylation status of KChIP2 determines its subcellular distribution in cardiac myocytes. Stress promotes nuclear entry of KChIP2, diverting it from ion channel modulation at the plasma membrane to other functions in the nuclear compartment.

Spatial Mapping of Hot-Spots at Lateral Heterogeneities in Monolayer Transition Metal Dichalcogenides.

Lateral heterogeneities in atomically thin 2D materials such as in-plane heterojunctions and grain boundaries (GBs) provide an extrinsic knob for manipulating the properties of nano- and optoelectronic devices and harvesting novel functionalities. However, these heterogeneities have the potential to adversely affect the performance and reliability of the 2D devices through the formation of nanoscopic hot-spots. In this report, scanning thermal microscopy (SThM) is utilized to map the spatial distribution of the temperature rise within monolayer transition metal dichalcogenide (TMD) devices upon dissipating a high electrical power through a lateral interface. The results directly demonstrate that lateral heterojunctions between MoS2 and WS2 do not largely impact the distribution of heat dissipation, while GBs of MoS2 appreciably localize heating in the device. High-resolution scanning transmission electron microscopy reveals that the atomic structure is nearly flawless around heterojunctions but can be quite defective near GBs. The results suggest that the interfacial atomic structure plays a crucial role in enabling uniform charge transport without inducing localized heating. Establishing such structure-property-processing correlation provides a better understanding of lateral heterogeneities in 2D TMD systems which is crucial in the design of future all-2D electronic circuitry with enhanced functionalities, lifetime, and performance.

Morphological Engineering of Winged Au@MoS2 Heterostructures for Electrocatalytic Hydrogen Evolution.

Molybdenum disulfide (MoS2) has been recognized as a promising cost-effective catalyst for water-splitting hydrogen production. However, the desired performance of MoS2 is often limited by insufficient edge-terminated active sites, poor electrical conductivity, and inefficient contact to the supporting substrate. To address these limitations, we developed a unique nanoarchitecture (namely, winged Au@MoS2 heterostructures enabled by our discovery of the "seeding effect" of Au nanoparticles for the chemical vapor deposition synthesis of vertically aligned few-layer MoS2 wings). The winged Au@MoS2 heterostructures provide an abundance of edge-terminated active sites and are found to exhibit dramatically improved electrocatalytic activity for the hydrogen evolution reaction. Theoretical simulations conducted for this unique heterostructure reveal that the hydrogen evolution is dominated by the proton adsorption step, which can be significantly promoted by introducing sufficient edge active sites. Our study introduces a new morphological engineering strategy to make the pristine MoS2 layered structures highly competitive earth-abundant catalysts for efficient hydrogen production.

Abrupt Thermal Shock of (NH4)2Mo3S13 Leads to Ultrafast Synthesis of Porous Ensembles of MoS2 Nanocrystals for High Gain Photodetectors.

Ultrafast synthesis of high-quality transition-metal dichalcogenide nanocrystals, such as molybdenum disulfide (MoS2), is technologically relevant for large-scale production of electronic and optoelectronic devices. Here, we report a rapid solid-state synthesis route for MoS2 using the chemically homogeneous molecular precursor, (NH4)2Mo3S13·H2O, resulting in nanoparticles with estimated size down to 25 nm only in 10 s at 1000 °C. Despite the extreme nonequilibrium conditions, the resulting porous MoS2 nanoparticles remain aggregated to preserve the form of the original rod shape bulk morphology of the molecular precursor. This ultrafast synthesis proceeds through the rapid decomposition of the precursor and rearrangement of Mo and S atoms coupled with simultaneous efficient release of massive gaseous species, to create nanoscale porosity in the resulting isomorphic pseudocrystals, which are composed of the MoS2 nanoparticles. Despite the very rapid escape of massive amounts of NH3, H2O, H2S, and S gases from the (NH4)2Mo3S13·H2O mm sized crystals, they retain their original shape as they convert to MoS2 rather than undergo explosive destruction from the rapid escape process of the gases. The obtained pseudocrystals are made of aggregated MoS2 nanocrystals exhibit a Brunauer-Emmett-Teller surface area of ∼35 m2/g with an adsorption average pore width of ∼160 Å. The nanoporous MoS2 crystals are solution processable by dispersing in ethanol and water and can be cast into large-area uniform composite films. Photodetectors fabricated from these films show more than 2 orders of magnitude higher conductivity (∼6.25 × 10-6 S/cm) and photoconductive gain (20 mA/W) than previous reports of MoS2 composite films. The optoelectronic properties of this nanoporous MoS2 imply that the shallow defects that originate from the ultrafast synthesis act as sensitizing centers that increase the photocurrent gain via two-level recombination kinetics.