Mapping Nanoscale Electrostatic Field Fluctuations around Graphene Dislocation Cores Using Four-Dimensional Scanning Transmission Electron Microscopy (4D-STEM).

Defects in crystalline lattices cause modulation of the atomic density, and this leads to variations in the associated electrostatics at the nanoscale. Mapping these spatially varying charge fluctuations using transmission electron microscopy has typically been challenging due to complicated contrast transfer inherent to conventional phase contrast imaging. To overcome this, we used four-dimensional scanning transmission electron microscopy (4D-STEM) to measure electrostatic fields near point dislocations in a monolayer. The asymmetry of the atomic density in a (1,0) edge dislocation core in graphene yields a local enhancement of the electric field in part of the dislocation core. Through experiment and simulation, the increased electric field magnitude is shown to arise from "long-range" interactions from beyond the nearest atomic neighbor. These results provide insights into the use of 4D-STEM to quantify electrostatics in thin materials and map out the lateral potential variations that are important for molecular and atomic bonding through Coulombic interactions.

Self-Compliant Threshold Switching Devices with High On/Off ratio by Control of Quantized Conductance in Ag Filaments.

Threshold switches based on conductive metal bridge devices are useful as selectors to block sneak leakage paths in memristor arrays used in neuromorphic computing and emerging nonvolatile memory. We demonstrate that control of Ag-cation concentration in Al2O3 electrolyte and Ag filament size and density play an important role in the high on/off ratio and self-compliance of metal-ion-based volatile threshold switching devices. To control Ag-cation diffusion, we inserted an engineered defective graphene monolayer between the Ag electrode and the Al2O3 electrolyte. The Ag-cation migration and the Ag filament size and density are limited by the pores in the defective graphene monolayer. This leads to quantized conductance in the Ag filaments and self-compliance resulting from the formation and dissolution of the Ag conductive filament.

Breastfeeding Ability After Breast Reductions: What does the Literature Tell us in 2023?

INTRODUCTION: Reduction mammaplasties are routinely performed on women of child-bearing age, yet there still exists some uncertainty regarding a patient's ability to breastfeed following the procedure. This is due to inconsistent definitions of "successful" breastfeeding, a variety of pedicles implemented, and inadequate follow-up in the published literature. Our aim was to summarize the current data and provide clear recommendations for counseling patients on expected breastfeeding outcomes following reduction mammaplasty. METHODS: A systematic review and meta-analysis in accordance with the PRISMA guidelines was conducted. We included papers that reported proportion of breastfeeding ability following reduction mammaplasty. RESULTS: We identified 33 papers that met our inclusion criteria. We found that women who undergo reduction mammaplasty are at a 3.5 times increased odds of not being able to breastfeed compared to controls. Overall, reduction mammaplasty patients have a breastfeeding success rate of 62%. The breastfeeding success rate for patients with inferior pedicles was 64%, superior pedicles was 59%, and lateral pedicles was 55%. No conclusions could be drawn regarding medial, central, vertical, and horizontal pedicles on breastfeeding ability. CONCLUSION: Current data suggest that women undergoing reduction mammaplasty have an increased odds of unsuccessful breastfeeding when compared to similar women who have not undergone the procedure. Based on the current literature, pedicle type does play a role in rate of breastfeeding success, although there is a need for further research on the aforementioned pedicles. Physicians should be aware of the likelihood of successful breastfeeding following reduction mammaplasty so that patients can be more thoroughly counseled prior to a decision for surgery. LEVEL OF EVIDENCE I: This journal requires that authors assign a level of evidence to each article. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors www.springer.com/00266 .

Discretized hexagonal boron nitride quantum emitters and their chemical interconversion.

Quantum emitters in two-dimensional hexagonal boron nitride (hBN) are of significant interest because of their unique photophysical properties, such as single-photon emission at room temperature, and promising applications in quantum computing and communications. The photoemission from hBN defects covers a wide range of emission energies but identifying and modulating the properties of specific emitters remain challenging due to uncontrolled formation of hBN defects. In this study, more than 2000 spectra are collected consisting of single, isolated zero-phonon lines (ZPLs) between 1.59 and 2.25 eV from diverse sample types. Most of ZPLs are organized into seven discretized emission energies. All emitters exhibit a range of lifetimes from 1 to 6 ns, and phonon sidebands offset by the dominant lattice phonon in hBN near 1370 cm-1. Two chemical processing schemes are developed based on water and boric acid etching that generate or preferentially interconvert specific emitters, respectively. The identification and chemical interconversion of these discretized emitters should significantly advance the understanding of solid-state chemistry and photophysics of hBN quantum emission.

Atomic-Level Dynamics of Point Vacancies and the Induced Stretched Defects in 2D Monolayer PtSe2.

Monolayer PtSe2 holds great potential in extending 2D devices functionality, but their atomic-level-defect study is still limited. Here, we investigate the atomic structures of lattice imperfections from point to stretched 1D defects in 1T-PtSe2 monolayers, using annular dark-field scanning transmission electron microscopy (ADF-STEM). We show Se vacancies (VSe) have preferential sites with high beam-induced mobility. Diverse divacancies form with paired VSe. We found stretched linear defects triggered by dynamics of VSe that altered strain fields, distinct from the line vacancies in 2H-phase 2D materials. The paired VSe stability and formation possibility of vacancy lines are evaluated by density functional theory. Lower sputtering energy in PtSe2 than that in MoS2 can cause larger possibility of atomic loss compared to diffusion required for creating VSe lines. This provides atomic insights into the defects in 1T-PtSe2 and shows how a deviated 1D structure is embedded in a 2D system without losing atom lines.

Waterproof molecular monolayers stabilize 2D materials.

Two-dimensional van der Waals materials have rich and unique functional properties, but many are susceptible to corrosion under ambient conditions. Here we show that linear alkylamines n-C m H2m+1NH2, with m = 4 through 11, are highly effective in protecting the optoelectronic properties of these materials, such as black phosphorus (BP) and transition-metal dichalcogenides (TMDs: WS2, 1T'-MoTe2, WTe2, WSe2, TaS2, and NbSe2). As a representative example, n-hexylamine (m = 6) can be applied in the form of thin molecular monolayers on BP flakes with less than 2-nm thickness and can prolong BP's lifetime from a few hours to several weeks and even months in ambient environments. Characterizations combined with our theoretical analysis show that the thin monolayers selectively sift out water molecules, forming a drying layer to achieve the passivation of the protected 2D materials. The monolayer coating is also stable in air, H2 annealing, and organic solvents, but can be removed by certain organic acids.

Nanoscale Bilayer Mechanical Lithography Using Water as Developer.

Sustainability has become a critical concern in the semiconductor industry as hazardous wastes released during the manufacturing process of semiconductor devices have an adverse impact on human beings and the environment. The use of hazardous solvents in existing fabrication processes also restricts the use of polymer substrates because of their low chemical resistance to such solvents. Here, we demonstrate an environmentally friendly mechanical, bilayer lithography that uses just water for development and lift-off. We show that we are able to create arbitrary patterns achieving resolution down to 310 nm. We then demonstrate the use of this technique to create functional devices by fabricating a MoS2 photodetector on a polyethylene terephthalate (PET) substrate with measured response times down to 42 ms.

Atomistic Mechanics of Torn Back Folded Edges of Triangular Voids in Monolayer WS2.

Triangular nanovoids in 2D materials transition metal dichalcogenides have vertex points that cause stress concentration and lead to sharp crack propagation and failure. Here, the atomistic mechanics of back folding around triangular nanovoids in monolayer WS2 sheets is examined. Combining atomic-resolution images from annular dark-field scanning transmission electron microscopy with reactive molecular modelling, it is revealed that the folding edge formation has statistical preferences under geometric conditions based on the orientation mismatch. It is further investigated how loading directions and strong interlayer friction, interplay with WS2 lattice's crack preference, govern the deformation and fracture pattern around folding edges. These results provide fundamental insights into the combination of fracture and folding in flexible monolayer crystals and the resultant Moiré lattices.

Atomically Precise Control of Carbon Insertion into hBN Monolayer Point Vacancies using a Focused Electron Beam Guide.

Precise controlled filling of point vacancies in hBN with carbon atoms is demonstrated using a focused electron beam method, which guides mobile C atoms into the desired defect site. Optimization of the technique enables the insertion of a single C atom into a selected monovacancy, and preferential defect filling with sub-2 nm accuracy. Increasing the C insertion process leads to thicker 3D C nanodots seeded at the hBN point vacancy site. Other light elements are also observed to bind to hBN vacancies, including O, opening up a wide range of complex defect structures that include B, C, N, and O atoms. The ability to selectively fill point vacancies in hBN with C atoms provides a pathway for creating non-hydrogenated covalently bonded C molecules embedded in the insulating hBN.

Self-Assembly of Bowlic Supramolecules on Graphene Imaged at the Individual Molecular Level using Heavy Atom Tagging.

The self-assembly of bowlic supramolecules on graphene surface is studied with single molecular sensitivity. This is achieved by incorporating a heavy metal tag in the form of a single W atom into the tip of the molecular structure, which enables the direct imaging of molecular distribution using annular dark-field scanning transmission electron microscopy (ADF-STEM) along with graphene as an electron transparent support. The bowlic molecules have nonplanar geometry, and their orientations with respect to their graphene substrate and with each other result in various packing configurations. Statistical data on intermolecular distances is obtained from numerous measurements of the bright contrast from the single metal atom tags. The analysis shows that the bowlic molecules lie sideways on the graphene surface with favorable head-to-tail stacking, rather than sitting vertically with the bowl facing toward the graphene surface. In thicker film regions, nanoscale lamellar fringes are observed, demonstrating that large-scale aligned packing extends into 3D. Image simulations and various molecular packing schemes are discussed to help interpret the ADF-STEM images and the possible range of molecular interactions occurring. These results aid the understanding of nonplanar supramolecular assemblies on van der Waals surfaces for potential applications in molecular recognition by porous films.

Controlling Photoluminescence Enhancement and Energy Transfer in WS2 :hBN:WS2 Vertical Stacks by Precise Interlayer Distances.

2D semiconducting transition metal dichalcogenides (TMDs) are endowed with fascinating optical properties especially in their monolayer limit. Insulating hBN films possessing customizable thickness can act as a separation barrier to dictate the interactions between TMDs. In this work, vertical layered heterostructures (VLHs) of WS2 :hBN:WS2 are fabricated utilizing chemical vapor deposition (CVD)-grown materials, and the optical performance is evaluated through photoluminescence (PL) spectroscopy. Apart from the prohibited indirect optical transition due to the insertion of hBN spacers, the variation in the doping level of WS2 drives energy transfer to arise from the layer with lower quantum efficiency to the other layer with higher quantum efficiency, whereby the total PL yield of the heterosystem is increased and the stack exhibits a higher PL intensity compared to the sum of those in the two WS2 constituents. Such doping effects originate from the interfaces that WS2 monolayers reside on and interact with. The electron density in the WS2 is also controlled and subsequent modulation of PL in the heterostructure is demonstrated by applying back-gated voltages. Other influential factors include the strain in WS2 and temperature. Being able to tune the energy transfer in the VLHs may expand the development of photonic applications in 2D systems.

Addressing the isomer cataloguing problem for nanopores in two-dimensional materials.

The presence of extended defects or nanopores in two-dimensional (2D) materials can change the electronic, magnetic and barrier membrane properties of the materials. However, the large number of possible lattice isomers of nanopores makes their quantitative study a seemingly intractable problem, confounding the interpretation of experimental and simulated data. Here we formulate a solution to this isomer cataloguing problem (ICP), combining electronic-structure calculations, kinetic Monte Carlo simulations, and chemical graph theory, to generate a catalogue of unique, most-probable isomers of 2D lattice nanopores. The results demonstrate remarkable agreement with precise nanopore shapes observed experimentally in graphene and show that the thermodynamic stability of a nanopore is distinct from its kinetic stability. Triangular nanopores prevalent in hexagonal boron nitride are also predicted, extending this approach to other 2D lattices. The proposed method should accelerate the application of nanoporous 2D materials by establishing specific links between experiment and theory/simulations, and by providing a much-needed connection between molecular design and fabrication.

Strong Opto-Structural Coupling in Low Dimensional GeSe3 Films.

Chalcogenide glasses as nanoscale thin films have become leading candidates for several optical and photonic technologies, ranging from reflective displays and filters to photonic memories. Current material systems, however, show strong optical absorption which limits their performance efficiencies and complicates device level integration. Herein, we report sputter deposited thin films of GeSe3, which are low loss and in which the flexible nature of the atomic structure results in thermally activated tunability in the refractive index as well as in the film's physical volume. Such changes, which occur beyond a threshold temperature are observed to be accumulative and directed toward a more equilibrium amorphous state of the film, instead of crystallization. Our results provide insight into a new type of configurability that is based on strong coupling in the material's opto-structural properties. The low optical losses in this material system combined with the tunability in the optical properties in the visible and near-infrared have direct application in higher performing optical coatings and in corrective optics.

Simultaneous Identification of Low and High Atomic Number Atoms in Monolayer 2D Materials Using 4D Scanning Transmission Electron Microscopy.

Simultaneous imaging of individual low and high atomic number atoms using annular dark field scanning transmission electron microscopy (ADF-STEM) is often challenging due to substantial differences in their scattering cross sections. This often leads to contrast from only the high atomic number species when imaged using ADF-STEM such as the Mo and 2S sites in monolayer MoS2 crystals, without detection of lighter atoms such as C, O, or N. Here, we show that by capturing an array of convergent beam electron diffraction patterns using a 2D pixelated electron detector (2D-PED) in a 4D STEM geometry enables identification of individual low and high atomic number atoms in 2D materials by multicomponent imaging. We have used ptychographic phase reconstructions, combined with angular dependent ADF-STEM reconstructions, to image light elements at lateral (nanopores) and vertical interfaces (surface dopants) within 2D monolayer MoS2. Differential phase contrast imaging (Div(DPC)) using quadrant segmentation of the 2D pixelated direct electron detector data not only qualitatively matches the ptychographic phase reconstructions in both resolution and contrast but also offers the additional potential for real time display. Using 4D-STEM, we have identified surface adatoms on MoS2 monolayers and have separated atomic columns with similar total atomic number into their relative combinations of low and high atomic number elements. These results demonstrate the rich information present in the data obtained during 4D-STEM imaging of ultrathin 2D materials and the ability of this approach to extract unique insights beyond conventional imaging.

MoS2 Liquid Cell Electron Microscopy Through Clean and Fast Polymer-Free MoS2 Transfer.

Two dimensional (2D) materials have found various applications because of their unique physical properties. For example, graphene has been used as the electron transparent membrane for liquid cell transmission electron microscopy (TEM) due to its high mechanical strength and flexibility, single-atom thickness, chemical inertness, etc. Here, we report using 2D MoS2 as a functional substrate as well as the membrane window for liquid cell TEM, which is enabled by our facile and polymer-free MoS2 transfer process. This provides the opportunity to investigate the growth of Pt nanocrystals on MoS2 substrates, which elucidates the formation mechanisms of such heterostructured 2D materials. We find that Pt nanocrystals formed in MoS2 liquid cells have a strong tendency to align their crystal lattice with that of MoS2, suggesting a van der Waals epitaxial relationship. Importantly, we can study its impact on the kinetics of the nanocrystal formation. The development of MoS2 liquid cells will allow further study of various liquid phenomena on MoS2, and the polymer-free MoS2 transfer process will be implemented in a wide range of applications.

Atomically Sharp Dual Grain Boundaries in 2D WS2 Bilayers.

It is shown that tilt grain boundaries (GBs) in bilayer 2D crystals of the transition metal dichalcogenide WS2 can be atomically sharp, where top and bottom layer GBs are located within sub-nanometer distances of each other. This expands the current knowledge of GBs in 2D bilayer crystals, beyond the established large overlapping GB types typically formed in chemical vapor deposition growth, to now include atomically sharp dual bilayer GBs. By using atomic-resolution annular dark-field scanning transmission electron microscopy (ADF-STEM) imaging, different atomic structures in the dual GBs are distinguished considering bilayers with a 3R (AB stacking)/2H (AA' stacking) interface as well as bilayers with 2H/2H boundaries. An in situ heating holder is used in ADF-STEM and the GBs are stable to at least 800 °C, with negligible thermally induced reconstructions observed. Normal dislocation cores are seen in one WS2 layer, but the second WS2 layer has different dislocation structures not seen in freestanding monolayers, which have metal-rich clusters to accommodate the stacking mismatch of the 2H:3R interface. These results reveal the competition between maintaining van der Waals bilayer stacking uniformity and dislocation cores required to stitch tilted bilayer GBs together.

Atomic structure of defects and dopants in 2D layered transition metal dichalcogenides.

Layered transition metal dichalcogenides (TMDs) offer monolayer 2D systems with diverse properties that extend beyond what graphene alone can achieve. The properties of TMDs are heavily influenced by the atomic structure and in particular imperfects in the crystallinity in the form of vacancy defects, grain boundaries, cracks, impurity dopants, ripples and edge terminations. This review will cover the current knowledge of the detailed structural forms of some of the most intensively studied 2D TMDs, such as MoS2, WSe2, MoTe2, WTe2, NbSe2, PtSe2, and also covers MXenes. The review will utilize results achieved using state-of-the-art aberration corrected transmission electron microscopy, including annular dark-field scanning transmission electron microscopy (ADF-STEM) and electron energy loss spectroscopy (EELS), showing how elemental discrimination can be achieved to understand structure at a deep level. The review will also cover the impact of single atom substitutional dopants, such as Cr, V and Mn, and electron energy loss spectroscopy used to understand the local bonding configuration. It is expected that this review will provide an atomic level understanding of 2D TMDs with a connection to imperfections that can arise from chemical vapour deposition synthesis, intentional doping, rips and tears, dislocations, strain, polycrystallinity and confinement to nanoribbons.

Revealing Strain-Induced Effects in Ultrathin Heterostructures at the Nanoscale.

Two-dimensional materials are being increasingly studied, particularly for flexible and wearable technologies because of their inherent thickness and flexibility. Crucially, one aspect where our understanding is still limited is on the effect of mechanical strain, not on individual sheets of materials, but when stacked together as heterostructures in devices. In this paper, we demonstrate the use of Kelvin probe microscopy in capturing the influence of uniaxial tensile strain on the band-structures of graphene and WS2 (mono- and multilayered) based heterostructures at high resolution. We report a major advance in strain characterization tools through enabling a single-shot capture of strain defined changes in a heterogeneous system at the nanoscale, overcoming the limitations (materials, resolution, and substrate effects) of existing techniques such as optical spectroscopy. Using this technique, we observe that the work-functions of graphene and WS2 increase as a function of strain, which we attribute to the Fermi level lowering from increased p-doping. We also extract the nature of the interfacial heterojunctions and find that they get strongly modulated from strain. We observe that the strain-enhanced charge transfer with the substrate plays a dominant role, causing the heterostructures to behave differently from two-dimensional materials in their isolated forms.

Geometrically Enhanced Thermoelectric Effects in Graphene Nanoconstrictions.

The influence of nanostructuring and quantum confinement on the thermoelectric properties of materials has been extensively studied. While this has made possible multiple breakthroughs in the achievable figure of merit, classical confinement, and its effect on the local Seebeck coefficient has mostly been neglected, as has the Peltier effect in general due to the complexity of measuring small temperature gradients locally. Here we report that reducing the width of a graphene channel to 100 nm changes the Seebeck coefficient by orders of magnitude. Using a scanning thermal microscope allows us to probe the local temperature of electrically contacted graphene two-terminal devices or to locally heat the sample. We show that constrictions in mono- and bilayer graphene facilitate a spatially correlated gradient in the Seebeck and Peltier coefficient, as evidenced by the pronounced thermovoltage Vth and heating/cooling response Δ TPeltier, respectively. This geometry dependent effect, which has not been reported previously in 2D materials, has important implications for measurements of patterned nanostructures in graphene and points to novel solutions for effective thermal management in electronic graphene devices or concepts for single material thermocouples.