Intrinsic and Strain-Dependent Properties of Suspended WSe2 Crystallites toward Next-Generation Nanoelectronics and Quantum-Enabled Sensors.

Two-dimensional (2D) layered materials exhibit great potential for high-performance electronics, where knowledge of their thermal and phononic properties is critical toward understanding heat dissipation mechanisms, considered to be a major bottleneck for current generation nanoelectronic, optoelectronic, and quantum-scale devices. In this work, noncontact Raman spectroscopy was used to analyze thermal properties of suspended 2D WSe2 membranes to access the intrinsic properties. Here, the influence of electron-phonon interactions within the parent crystalline WSe2 membranes was deciphered through a comparative analysis of extrinsic substrate-supported WSe2, where heat dissipation mechanisms are intimately tied to the underlying substrate. Moreover, the excitonic states in WSe2 were analyzed by using temperature-dependent photoluminescence spectroscopy, where an enhancement in intensity of the localized excitons in suspended WSe2 was evident. Finally, phononic and electronic properties in suspended WSe2 were examined through nanoscale local strain engineering, where a uniaxial force was induced on the membrane using a Au-coated cantilever within an atomic force microscope. Through the fundamental analysis provided here with temperature and strain-dependent phononic and optoelectronic properties in suspended WSe2 nanosheets, the findings will inform the design of next-generation energy-efficient, high-performance devices based on WSe2 and other 2D materials, including for quantum applications.

Non-Linear Optics at Twist Interfaces in h-BN/SiC Heterostructures.

Understanding the emergent electronic structure in twisted atomically thin layers has led to the exciting field of twistronics. However, practical applications of such systems are challenging since the specific angular correlations between the layers must be precisely controlled and the layers have to be single crystalline with uniform atomic ordering. Here, an alternative, simple, and scalable approach is suggested, where nanocrystallinetwo-dimensional (2D) film on 3D substrates yields twisted-interface-dependent properties. Ultrawide-bandgap hexagonal boron nitride (h-BN) thin films are directly grown on high in-plane lattice mismatched wide-bandgap silicon carbide (4H-SiC) substrates to explore the twist-dependent structure-property correlations. Concurrently, nanocrystalline h-BN thin film shows strong non-linear second-harmonic generation and ultra-low cross-plane thermal conductivity at room temperature, which are attributed to the twisted domain edges between van der Waals stacked nanocrystals with random in-plane orientations. First-principles calculations based on time-dependent density functional theory manifest strong even-order optical nonlinearity in twisted h-BN layers. This work unveils that directly deposited 2D nanocrystalline thin film on 3D substrates could provide easily accessible twist-interfaces, therefore enabling a simple and scalable approach to utilize the 2D-twistronics integrated in 3D material devices for next-generation nanotechnology.

On the electronic and spin-valley coupling of vanadium doped MoS2(1-x)Se2xmonolayers.

Monolayers of MoS2with tunable bandgap and valley positions are highly demanding for their applications in opto-spintronics. Herein, selenium (Se) and vanadium (V) co-doped MoS2monolayers (vanadium doped MoS2(1-x)Se2x(V-MoSSe)) are developed and showed their variations in the electronic and optical properties with dopant content. Vanadium gets substitutionally (in place of Mo) doped within the MoS2lattice while selenium doped in place of sulfur, as shown by a detailed microstructure and spectroscopy analyses. The bandgap tunability with selenium doping can be achieved while valley shift is occurred due to the doping of vanadium. Chemical vapor deposition assisted grown MoS2(also selenium doped MoS2as shown here) is known for its n-type transport behavior while vanadium doping is found to be changing its nature to p-doping. Chirality dependent photoexcitation studies indicate a room temperature valley splitting in V-MoSSe (∼8 meV), where such a valley splitting is verified using density functional theory based calculations.

Soft pinning: Experimental validation of static correlations in supercooled molecular glass-forming liquids.

Enormous enhancement in the viscosity of a liquid near its glass transition is a hallmark of glass transition. Within a class of theoretical frameworks, it is connected to growing many-body static correlations near the transition, often called "amorphous ordering." At the same time, some theories do not invoke the existence of such a static length scale in the problem. Thus, proving the existence and possible estimation of the static length scales of amorphous order in different glass-forming liquids is very important to validate or falsify the predictions of these theories and unravel the true physics of glass formation. Experiments on molecular glass-forming liquids become pivotal in this scenario as the viscosity grows several folds (∼1014), and simulations or colloidal glass experiments fail to access these required long-time scales. Here we design an experiment to extract the static length scales in molecular liquids using dilute amounts of another large molecule as a pinning site. Results from dielectric relaxation experiments on supercooled Glycerol with different pinning concentrations of Sorbitol and Glucose, as well as the simulations on a few model glass-forming liquids with pinning sites, indicate the versatility of the proposed method, opening possible new avenues to study the physics of glass transition in other molecular liquids.

Heteroatom Functionalization of H-Terminated Diamond Surfaces.

Diamond surface functionalization has received significant research interest recently. Specifically, H-termination has been widely adopted because it endows the diamond surface with negative electron affinity and the hole carrier is injected in the presence of surface transfer dopants. Exploring different functional groups' attachment on diamond surfaces and their impact on the electronic structure, using wet and dry chemical approaches, would hence be of interest in engineering diamond as a semiconductor. Here, we report the functionalization of the H-terminated diamond surface with nitrogen and sulfur heteroatoms. Surface characterization of functionalized diamond surfaces shows that these groups are well-distributed and covalently bonded to diamonds. Four chemical functional groups (-SH, -S-S-, -S-O, and -S=O) were found on the sulfurized diamond surface, and two groups (-NH2 and =NH) upon amination. We also report co-functionalization of surface with N and S (N-S), where sulfurization promotes sequential amination efficiency with reduced exposure time. Electrical measurement shows that heteroatom-modified diamond surfaces possess higher conductivity than H-terminated diamonds. Density functional theory (DFT) shows that upon functionalization with various N/S ratios, the conduction band minimum and valence band maximum downshift, which lowers the bandgap in comparison to an H-terminated diamond. These observations suggest the possibility of heteroatom functionalizations with enhanced surface electrical conductivity on the diamond that are useful for various electronic applications.

Phase Stability of Hexagonal/Cubic Boron Nitride Nanocomposites.

Boron nitride (BN) is an exceptional material, and among its polymorphs, two-dimensional (2D) hexagonal and three-dimensional (3D) cubic BN (h-BN and c-BN) phases are most common. The phase stability regimes of these BN phases are still under debate, and phase transformations of h-BN/c-BN remain a topic of interest. Here, we investigate the phase stability of 2D/3D h-BN/c-BN nanocomposites and show that the coexistence of two phases can lead to strong nonlinear optical properties and low thermal conductivity at room temperature. Furthermore, spark-plasma sintering of the nanocomposite shows complete phase transformation to 2D h-BN with improved crystalline quality, where 3D c-BN possibly governs the nucleation and growth kinetics. Our demonstration might be insightful in phase engineering of BN polymorph-based nanocomposites with desirable properties for optoelectronics and thermal energy management applications.

Unravelling the room temperature growth of two-dimensional h-BN nanosheets for multifunctional applications.

The room temperature growth of two-dimensional van der Waals (2D-vdW) materials is indispensable for state-of-the-art nanotechnology. Low temperature growth supersedes the requirement of elevated growth temperatures accompanied with high thermal budgets. Moreover, for electronic applications, low or room temperature growth reduces the possibility of intrinsic film-substrate interfacial thermal diffusion related deterioration of the functional properties and the consequent deterioration of the device performance. Here, we demonstrated the growth of ultrawide-bandgap boron nitride (BN) at room temperature by using the pulsed laser deposition (PLD) process, which exhibited various functional properties for potential applications. Comprehensive chemical, spectroscopic and microscopic characterizations confirmed the growth of ordered nanosheet-like hexagonal BN (h-BN). Functionally, the nanosheets show hydrophobicity, high lubricity (low coefficient of friction), and a low refractive index within the visible to near-infrared wavelength range, and room temperature single-photon quantum emission. Our work unveils an important step that brings a plethora of potential applications for these room temperature grown h-BN nanosheets as the synthesis can be feasible on any given substrate, thus creating a scenario for "h-BN on demand" under a frugal thermal budget.

Realizing Quantum Technologies in Nanomaterials and Nanoscience.

A brief overview of quantum materials and their prospects for applications, in the near, mid, and far-term in the areas of quantum information science, spintronics, valleytronics, and twistronics and those involving topology are covered in this perspective. The material and processing challenges that will modulate the realism of the applications will be discussed as well.

Deterministic fabrication of 3D/2D perovskite bilayer stacks for durable and efficient solar cells.

Realizing solution-processed heterostructures is a long-enduring challenge in halide perovskites because of solvent incompatibilities that disrupt the underlying layer. By leveraging the solvent dielectric constant and Gutmann donor number, we could grow phase-pure two-dimensional (2D) halide perovskite stacks of the desired composition, thickness, and bandgap onto 3D perovskites without dissolving the underlying substrate. Characterization reveals a 3D-2D transition region of 20 nanometers mainly determined by the roughness of the bottom 3D layer. Thickness dependence of the 2D perovskite layer reveals the anticipated trends for n-i-p and p-i-n architectures, which is consistent with band alignment and carrier transport limits for 2D perovskites. We measured a photovoltaic efficiency of 24.5%, with exceptional stability of T99 (time required to preserve 99% of initial photovoltaic efficiency) of >2000 hours, implying that the 3D/2D bilayer inherits the intrinsic durability of 2D perovskite without compromising efficiency.

Piezoelectricity across 2D Phase Boundaries.

Piezoelectricity in low-dimensional materials and metal-semiconductor junctions has attracted recent attention. Herein, a 2D in-plane metal-semiconductor junction made of multilayer 2H and 1T' phases of molybdenum(IV) telluride (MoTe2 ) is investigated. Strong piezoelectric response is observed using piezoresponse force microscopy at the 2H-1T' junction, despite that the multilayers of each individual phase are weakly piezoelectric. The experimental results and density functional theory calculations suggest that the amplified piezoelectric response observed at the junction is due to the charge transfer across the semiconducting and metallic junctions resulting in the formation of dipoles and excess charge density, allowing the engineering of piezoelectric response in atomically thin materials.

Sustainable Biocomposites for Structural Applications with Environmental Affinity.

In this work, we report a facile preparation of biocomposites using a chitosan matrix that is reinforced with morphed graphene in amounts from 1 to 5 wt % C. The composites are processed by milling and conventional sintering. The morphed graphene additions show clear improvements in mechanical properties, having a direct correlation with temperature in particular for 180 °C. Higher temperatures are detrimental to chitosan and the properties drop because chitosan degrades. Mechanical properties in the composite such as yield strength and compressive strength increase between 40 and 50% with respect to the pure chitosan samples. The Young's modulus presents a drop of approximately 10%, but the fracture toughness increases up to 3.5 fold. The properties of our sustainable composites are comparable to those seen in polymers such as polyethylene, polypropylene, nylon, and poly(methyl methacrylate), among other commodity or single use plastics. The enhancement in the mechanical properties is attributed to the morphed graphene embedded chitosan matrix that generates a network of intergranular "anchors" that hold the chitosan crystals in place, preventing failure. The composites can be molded into near-net-shape products, machined, or shaped using various methods including laser lithography. These studies demonstrate the feasibility of fabricating biocomposites with different architectures and sizes for disposable structural components. Both chitosan and the composites are compostable and biodegradable with the potential to sustain plant growth when discarded. In addition, morphed graphene and chitosan are produced from byproducts or waste, which may result in a negative carbon footprint on the environment.

Photo Rechargeable Li-Ion Batteries Using Nanorod Heterostructure Electrodes.

New ways of directly using solar energy to charge electrochemical energy storage devices such as batteries would lead to exciting developments in energy technologies. Here, a two-electrode photo rechargeable Li-ion battery is demonstrated using nanorod of type II semiconductor heterostructures with in-plane domains of crystalline MoS2 and amorphous MoOx . The staggered energy band alignment of MoS2 and MoOx limits the electron holes recombination and causes holes to be retained in the Li intercalated MoS2 electrode. The holes generated in the MoS2 pushes the intercalated Li-ions and hence charge the battery. Low band gap, high efficiency photo-conversion and efficient electron-hole separation help the battery to fully charge within a few hours using solar light. The proposed concept and materials can enable next generation stable photo-rechargeable battery electrodes, in contrast to the reported materials.

Friction of magnetene, a non-van der Waals 2D material.

Two-dimensional (2D) materials are known to have low-friction interfaces by reducing the energy dissipated by sliding contacts. While this is often attributed to van der Waals (vdW) bonding of 2D materials, nanoscale and quantum confinement effects can also act to modify the atomic interactions of a 2D material, producing unique interfacial properties. Here, we demonstrate the low-friction behavior of magnetene, a non-vdW 2D material obtained via the exfoliation of magnetite, showing statistically similar friction to benchmark vdW 2D materials. We find that this low friction is due to 2D confinement effects of minimized potential energy surface corrugation, lowered valence states reducing surface adsorbates, and forbidden low-damping phonon modes, all of which contribute to producing a low-friction 2D material.

Corrosion Resistance of Sulfur-Selenium Alloy Coatings.

Despite decades of research, metallic corrosion remains a long-standing challenge in many engineering applications. Specifically, designing a material that can resist corrosion both in abiotic as well as biotic environments remains elusive. Here a lightweight sulfur-selenium (S-Se) alloy is designed with high stiffness and ductility that can serve as an excellent corrosion-resistant coating with protection efficiency of ≈99.9% for steel in a wide range of diverse environments. S-Se coated mild steel shows a corrosion rate that is 6-7 orders of magnitude lower than bare metal in abiotic (simulated seawater and sodium sulfate solution) and biotic (sulfate-reducing bacterial medium) environments. The coating is strongly adhesive, mechanically robust, and demonstrates excellent damage/deformation recovery properties, which provide the added advantage of significantly reducing the probability of a defect being generated and sustained in the coating, thus improving its longevity. The high corrosion resistance of the alloy is attributed in diverse environments to its semicrystalline, nonporous, antimicrobial, and viscoelastic nature with superior mechanical performance, enabling it to successfully block a variety of diffusing species.

Structure, Properties and Applications of Two-Dimensional Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) has emerged as a strong candidate for two-dimensional (2D) material owing to its exciting optoelectrical properties combined with mechanical robustness, thermal stability, and chemical inertness. Super-thin h-BN layers have gained significant attention from the scientific community for many applications, including nanoelectronics, photonics, biomedical, anti-corrosion, and catalysis, among others. This review provides a systematic elaboration of the structural, electrical, mechanical, optical, and thermal properties of h-BN followed by a comprehensive account of state-of-the-art synthesis strategies for 2D h-BN, including chemical exfoliation, chemical, and physical vapor deposition, and other methods that have been successfully developed in recent years. It further elaborates a wide variety of processing routes developed for doping, substitution, functionalization, and combination with other materials to form heterostructures. Based on the extraordinary properties and thermal-mechanical-chemical stability of 2D h-BN, various potential applications of these structures are described.

Deformation resilient cement structures using 3D-printed molds.

Cementitious structures exhibit high compression strength but suffer from inherent brittleness. Conversely, nature creates structures using mostly brittle phases that overcome the strength-toughness trade-off, mainly through internalized packaging of brittle phases with soft organic binders. Here, we develop complex architectures of cementitious materials using an inverse replica approach where a soft polymer phase emerges as an external conformal coating. Architected polymer templates are printed, cement pastes are molded into these templates, and cementitious structures with thin polymer surface coating are achieved after the solubilization of sacrificial templates. These polymer-coated architected cementitious structures display unusual mechanical behavior with considerably higher toughness compared to conventional non-porous structures. They resist catastrophic failure through delayed damage propagation. Most interestingly, the architected structures show significant deformation recovery after releasing quasi-static loading, atypical in conventional cementitious structures. This approach allows a simple strategy to build more deformation resilient cementitious structures than their traditional counterparts.

Light-Assisted Rechargeable Lithium Batteries: Organic Molecules for Simultaneous Energy Harvesting and Storage.

Lithium batteries that could be charged on exposure to sunlight will bring exciting new energy storage technologies. Here, we report a photorechargeable lithium battery employing nature-derived organic molecules as a photoactive and lithium storage electrode material. By absorbing sunlight of a desired frequency, lithiated tetrakislawsone electrodes generate electron-hole pairs. The holes oxidize the lithiated tetrakislawsone to tetrakislawsone while the generated electrons flow from the tetrakislawsone cathode to the Li metal anode. During electrochemical operation, the observed rise in charging current, specific capacity, and Coulombic efficiency under light irradiation in contrast to the absence of light indicates that the quinone-based organic electrode is acting as both photoactive and lithium storage material. Careful selection of electrode materials with optimal bandgap to absorb the intended frequency of sunlight and functional groups to accept Li-ions reversibly is a key to the progress of solar rechargeable batteries.

Scale-Enhanced Magnetism in Exfoliated Atomically Thin Magnetite Sheets.

The discovery of ferromagnetism in atomically thin layers at room temperature widens the prospects of 2D materials for device applications. Recently, two independent experiments demonstrated magnetic ordering in two dissimilar 2D systems, CrI3 and Cr2 Ge2 Te6 , at low temperatures and in VSe2 at room temperature, but observation of intrinsic room-temperature magnetism in 2D materials is still a challenge. Here a transition at room temperature that increases the magnetization in magnetite while thinning down the bulk material to a few atom-thick sheets is reported. DC magnetization measurements prove ferrimagnetic ordering with increased magnetization and density functional theory calculations ascribe their origin to the low dimensionality of the magnetite layers. In addition, surface energy calculations for different cleavage planes in passivated magnetite crystal agree with the experimental observations of obtaining 2D sheets from non-van der Waals crystals.

Lithium, sodium and magnesium ion conduction in solid state mixed polymer electrolytes.

Alkali and alkaline earth metal-ion batteries are currently among the most efficient electrochemical energy storage devices. However, their stability and safety performance are greatly limited when used with volatile organic liquid electrolytes. A solid state polymer electrolyte is a prospective solution even though poor ionic conductivity at room temperature remains a bottleneck. Here we propose the mixing of two similar polymer matrices, poly(dimethyl siloxane) and poly(ethylene oxide), to address this challenge. The resulting electrolyte matrix is denser and significantly improves room-temperature ionic conductivity. Ab initio analyses of the reaction between the cations and the polymers show that oxygen sites act as entrapment sites for the cations and that ionic conduction likely occurs through hopping between adjacent oxygen sites. Molecular dynamics simulations of the dynamics of both polymers and the dynamics of the polymer mix show that the more frequent and more pronounced molecular vibrations of the polymer mix are likely responsible for reducing the time between two consecutive oxygen entrapments, thereby speeding up the conduction process. This hypothesis is experimentally validated by the practically useful ionic conductivity (σ≈ 10-4 S cm-1 at 25 °C) and the improved safety parameters exhibited by a transparent flexible multi-cation (Li+, Na+ and Mg2+) conducting solid channel made up of the above mixed polymer system.

2D Electrets of Ultrathin MoO2 with Apparent Piezoelectricity.

Since graphene, a variety of 2D materials have been fabricated in a quest for a tantalizing combination of properties and desired physiochemical behavior. 2D materials that are piezoelectric, i.e., that allow for a facile conversion of electrical energy into mechanical and vice versa, offer applications for sensors, actuators, energy harvesting, stretchable and flexible electronics, and energy storage, among others. Unfortunately, materials must satisfy stringent symmetry requirements to be classified as piezoelectric. Here, 2D ultrathin single-crystal molybdenum oxide (MoO2 ) flakes that exhibit unexpected piezoelectric-like response are fabricated, as MoO2 is centrosymmetric and should not exhibit intrinsic piezoelectricity. However, it is demonstrated that the apparent piezoelectricity in 2D MoO2 emerges from an electret-like behavior induced by the trapping and stabilization of charges around defects in the material. Arguably, the material represents the first 2D electret material and suggests a route to artificially engineer piezoelectricity in 2D crystals. Specifically, it is found that the maximum out-of-plane piezoresponse is 0.56 pm V-1 , which is as strong as that observed in conventional 2D piezoelectric materials. The charges are found to be highly stable at room temperature with a trapping energy barrier of ≈2 eV.