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Defect engineering of van der Waals semiconductors has been demonstrated as an effective approach to manipulate the structural and functional characteristics toward dynamic device controls, yet correlations between physical properties with defect evolution remain underexplored. Using proton irradiation, we observe an enhanced exciton-to-trion conversion of the atomically thin WS2. The altered excitonic states are closely correlated with nanopore induced atomic displacement, W nanoclusters, and zigzag edge terminations, verified by scanning transmission electron microscopy, photoluminescence, and Raman spectroscopy. Density functional theory calculation suggests that nanopores facilitate formation of in-gap states that act as sinks for free electrons to couple with excitons. The ion energy loss simulation predicts a dominating electron ionization effect upon proton irradiation, providing further evidence on band perturbations and nanopore formation without destroying the overall crystallinity. This study provides a route in tuning the excitonic properties of van der Waals semiconductors using an irradiation-based defect engineering approach.
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In a scanning transmission electron microscope (STEM), producing a high-resolution image generally requires an electron beam focused to the smallest point possible. However, the magnetic lenses used to focus the beam are unavoidably imperfect, introducing aberrations that limit resolution. Modern STEMs overcome this by using hardware aberration correctors comprised of many multipole elements, but these devices are complex, expensive, and can be difficult to tune. We demonstrate a design for an electrostatic phase plate that can act as an aberration corrector. The corrector is comprised of annular segments, each of which is an independent two-terminal device that can apply a constant or ramped phase shift to a portion of the electron beam. We show the improvement in image resolution using an electrostatic corrector. Engineering criteria impose that much of the beam within the probe-forming aperture be blocked by support bars, leading to large probe tails for the corrected probe that sample the specimen beyond the central lobe. We also show how this device can be used to create other STEM beam profiles such as vortex beams and probes with a high degree of phase diversity, which improve information transfer in ptychographic reconstructions.
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Using four-dimensional scanning transmission electron microscopy, we demonstrate a method to visualize grains and grain boundaries in WSe2 grown by metal organic chemical vapor deposition (MOCVD) directly onto silicon dioxide. Despite the chemical purity and uniform thickness and texture of the MOCVD-grown WSe2, we observe a high density of small grains that corresponds with the overall selenium deficiency we measure through ion beam analysis. Moreover, reconstruction of grain information permits the creation of orientation maps that demonstrate the nucleation mechanism for new layers-triangular domains with the same orientation as the layer underneath induces a tensile strain increasing the lattice parameter at these sites.
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Strain engineering provides an effective way of tailoring the electronic and optoelectronic properties of semiconductor nanomaterials and nanodevices, giving rise to novel functionalities. Here, we present direct experimental evidence of strain-induced modifications of hole mobility in individual gallium arsenide (GaAs) nanowires, using in situ transmission electron microscopy (TEM). The conductivity of the nanowires varied with applied uniaxial tensile stress, showing an initial decrease of â¼5-20% up to a stress of 1-2 GPa, subsequently increasing up to the elastic limit of the nanowires. This is attributed to a hole mobility variation due to changes in the valence band structure caused by stress and strain. The corresponding lattice strain in the nanowires was quantified by in situ four dimensional scanning TEM and showed a complex spatial distribution at all stress levels. Meanwhile, a significant red shift of the band gap induced by the stress and strain was unveiled by monochromated electron energy loss spectroscopy.
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Scanning transmission electron microscopy (STEM) allows for imaging, diffraction, and spectroscopy of materials on length scales ranging from microns to atoms. By using a high-speed, direct electron detector, it is now possible to record a full two-dimensional (2D) image of the diffracted electron beam at each probe position, typically a 2D grid of probe positions. These 4D-STEM datasets are rich in information, including signatures of the local structure, orientation, deformation, electromagnetic fields, and other sample-dependent properties. However, extracting this information requires complex analysis pipelines that include data wrangling, calibration, analysis, and visualization, all while maintaining robustness against imaging distortions and artifacts. In this paper, we present py4DSTEM, an analysis toolkit for measuring material properties from 4D-STEM datasets, written in the Python language and released with an open-source license. We describe the algorithmic steps for dataset calibration and various 4D-STEM property measurements in detail and present results from several experimental datasets. We also implement a simple and universal file format appropriate for electron microscopy data in py4DSTEM, which uses the open-source HDF5 standard. We hope this tool will benefit the research community and help improve the standards for data and computational methods in electron microscopy, and we invite the community to contribute to this ongoing project.
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Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light-emitting applications. Recent studies have focused on nanoplatelets that are able to self-assemble and transform on solid substrates. However, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present a detailed analysis of the transformation of self-assembled stacks of CsPbBr3 nanoplatelets in solution over a period of a few months by using ex situ transmission electron microscopy and surface analysis. We demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: (i) desorption of the ligands from the surfaces of the particles, causing the seamless atomic merging of nanoplatelet stacks into nanobelts; (ii) merging of neighboring nanobelts that form more extended nanoplates; and (iii) attachment of nanobelts and nanoplates, forming objects with an atomic structure that resembles a mosaic made of broken nanotiles. We reveal that aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr, with the atomic columns of neighboring perovskite lattices shifted by a half-unit-cell, forming Ruddlesden-Popper planar faults. We also show, via in situ monitoring of the nanocrystal photoluminescence combined with transmission electron microscopy analysis, that the transformation is temperature driven and that it can take place within tens of minutes in solution and in spin-coated films. Understanding this process gives crucial information for the design and fabrication of perovskite materials, where control over the type and density of defects is desired, stimulating the development of perovskite nanocrystal structures with tailored electronic properties.
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Large-pore mesoporous silica nanoparticles (MSN) were prepared and functionalized to serve as a highly robust and biocompatible delivery platform for platinum-acridine (PA) anticancer agents. The material showed a high loading capacity for the dicationic, hydrophilic hybrid agent [PtCl(en)(N-[acridin-9-ylaminoethyl]-N-methylpropionamidine)] dinitrate salt (P1A1) and virtually complete retention of payload at neutral pH in a high-chloride buffer. In acidic media mimicking the pH inside the cell lysosomes, rapid, burst-like release of P1A1 from the nanoparticles is observed. Coating of the materials in phospholipid bilayers resulted in nanoparticles with greatly improved colloidal stability. The lipid and carboxylate-modified nanoparticles containing 40â wt % drug caused S-phase arrest and inhibited cell proliferation in pancreatic cancer cells at submicromolar concentrations similar to carrier-free P1A1. The most striking feature of nanoparticle-delivered P1A1 was that the payload did not escape from the acidified lysosomal vesicles into the cytoplasm, but was shuttled to the nuclear membrane and released into the nucleus.
Assuntos
Acridinas/química , Antineoplásicos/química , Complexos de Coordenação/química , Portadores de Fármacos/química , Nanopartículas/química , Platina , Dióxido de Silício/química , Acridinas/farmacologia , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/farmacologia , Liberação Controlada de Fármacos , Humanos , Concentração de Íons de Hidrogênio , Microscopia Eletrônica de Transmissão/métodos , Tamanho da Partícula , Fosfolipídeos/química , Polietilenoglicóis/química , Porosidade , Propriedades de SuperfícieRESUMO
Transition metal dichalcogenides (TMDCs), such as MoS2 and WSe2, are free of dangling bonds and therefore make more "ideal" Schottky junctions than bulk semiconductors, which produce Fermi energy pinning and recombination centers at the interface with bulk metals, inhibiting charge transfer. Here, we observe a more than 10× enhancement in the indirect band gap photoluminescence of transition metal dichalcogenides (TMDCs) deposited on various metals (e.g., Cu, Au, Ag), while the direct band gap emission remains unchanged. We believe the main mechanism of light emission arises from photoexcited hot electrons in the metal that are injected into the conduction band of MoS2 and WSe2 and subsequently recombine radiatively with minority holes in the TMDC. Since the conduction band at the K-point is 0.5 eV higher than at the Σ-point, a lower Schottky barrier exists for the Σ-point band, making electron injection more favorable. Also, the Σ band consists of the sulfur pz orbital, which overlaps more significantly with the electron wave functions in the metal. This enhancement in the indirect emission only occurs for thick flakes of MoS2 and WSe2 (≥100 nm) and is completely absent in monolayer and few-layer (â¼10 nm) flakes. Here, the flake thickness must exceed the depletion width of the Schottky junction, in order for efficient radiative recombination to occur in the TMDC. The intensity of this indirect peak decreases at low temperatures, which is consistent with the hot electron injection model.
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We investigate the role of weak clamping forces, typically assumed to be infinite, in carbon nanotube mechanical resonators. Due to these forces, we observe a hysteretic clamping and unclamping of the nanotube device that results in a discrete drop in the mechanical resonance frequency on the order of 5-20 MHz, when the temperature is cycled between 340 and 375 K. This instability in the resonant frequency results from the nanotube unpinning from the electrode/trench sidewall where it is bound weakly by van der Waals forces. Interestingly, this unpinning does not affect the Q-factor of the resonance, since the clamping is still governed by van der Waals forces above and below the unpinning. For a 1 µm device, the drop observed in resonance frequency corresponds to a change in nanotube length of approximately 50-65 nm. On the basis of these findings, we introduce a new model, which includes a finite tension around zero gate voltage due to van der Waals forces and shows better agreement with the experimental data than the perfect clamping model. From the gate dependence of the mechanical resonance frequency, we extract the van der Waals clamping force to be 1.8 pN. The mechanical resonance frequency exhibits a striking temperature dependence below 200 K attributed to a temperature-dependent slack arising from the competition between the van der Waals force and the thermal fluctuations in the suspended nanotube.
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We investigate the electronic and optoelectronic properties of quasi-metallic nanotube pn-devices, which have smaller band gaps than most known bulk semiconductors. These carbon nanotube-based devices deviate from conventional bulk semiconductor device behavior due to their low-dimensional nature. We observe rectifying behavior based on Zener tunneling of ballistic carriers instead of ideal diode behavior, as limited by the diffusive transport of carriers. We observe substantial photocurrents at room temperature, suggesting that these quasi-metallic pn-devices may have a broader impact in optoelectronic devices. A new technique based on photocurrent spectroscopy is presented to identify the unique chirality of nanotubes in a functional device. This chirality information is crucial in obtaining a theoretical understanding of the underlying device physics that depends sensitively on nanotube chirality, as is the case for quasi-metallic nanotube devices. A detailed model is developed to fit the observed I-V characteristics, which enables us to verify the band gap from these measurements as well as the dimensions of the insulating tunneling barrier region.
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In conventional ferroelectric materials, polarization is an intrinsic property limited by bulk crystallographic structure and symmetry. Recently, it has been demonstrated that polar order can also be accessed using inherently non-polar van der Waals materials through layer-by-layer assembly into heterostructures, wherein interfacial interactions can generate spontaneous, switchable polarization. Here we show that deliberate interlayer rotations in multilayer van der Waals heterostructures modulate both the spatial ordering and switching dynamics of polar domains. The engendered tunability is unparalleled in conventional bulk ferroelectrics or polar bilayers. By means of operando transmission electron microscopy we show how alterations of the relative rotations of three WSe2 layers produce structural polytypes with distinct arrangements of polar domains with either a global or localized switching response. Furthermore, the presence of uniaxial strain generates structural anisotropy that yields a range of switching behaviours, coercivities and even tunable biased responses. We also provide evidence of mechanical coupling between the two interfaces of the trilayer, a key consideration for the control of switching dynamics in polar multilayer structures more broadly.
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Current reports of thermal expansion coefficients (TEC) of two-dimensional (2D) materials show large discrepancies that span orders of magnitude. Determining the TEC of any 2D material remains difficult due to approaches involving indirect measurement of samples that are atomically thin and optically transparent. We demonstrate a methodology to address this discrepancy and directly measure TEC of nominally monolayer epitaxial WSe2 using four-dimensional scanning transmission electron microscopy (4D-STEM). Experimentally, WSe2 from metal-organic chemical vapor deposition (MOCVD) was heated through a temperature range of 18-564 °C using a barrel-style heating sample holder to observe temperature-induced structural changes without additional alterations or destruction of the sample. By combining 4D-STEM measurements with quantitative structural analysis, the thermal expansion coefficient of nominally monolayer polycrystalline epitaxial 2D WSe2 was determined to be (3.5 ± 0.9) × 10-6 K-1 and (5.7 ± 2) × 10-5 K-1 for the in- and out-of-plane TEC, respectively, and (3.6 ± 0.2) × 10-5 K-1 for the unit cell volume TEC, in good agreement with historically determined values for bulk crystals.
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The manipulation of nano-objects through heating is an effective strategy for inducing structural modifications and therefore changing the optoelectronic properties of semiconducting materials. Despite its potential, the underlying mechanism of the structural transformations remains elusive, largely due to the challenges associated with their in situ observations. To address these issues, we synthesize temperature-sensitive CsPbBr3 perovskite nanoplatelets and investigate their structural evolution at the nanoscale using in situ heating transmission electron microscopy. We observe the morphological changes that start from the self-assembly of the nanoplatelets into ribbons on a substrate. We identify several paths of merging nanoplates within ribbons that ultimately lead to the formation of nanosheets dispersed randomly on the substrate. These observations are supported by molecular dynamics simulations. We correlate the various paths for merging to the random orientation of the initial ribbons along with the ligand mobility (especially from the edges of the nanoplatelets). This leads to the preferential growth of individual nanosheets and the merging of neighboring ones. These processes enable the creation of structures with tunable emission, ranging from blue to green, all from a single material. Our real-time observations of the transformation of perovskite 2D nanocrystals reveal a route to achieve large-area nanosheets by controlling the initial orientation of the self-assembled objects with potential for large-scale applications.
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With the rapid increase in the use of lithium-ion batteries (LIBs), the development of safe LIBs has become an important social issue. Replacing flammable organic liquid electrolytes in current LIBs with water can be an alternative route to resolve this safety concern. The water-in-salt (WIS) electrolytes received great attention as next-generation electrolytes due to their large electrochemical stability window. However, their high cathodic limit remains as a challenge, impeding the use of low-potential anodes. Here, we report the first biodirected synthesis of carbonaceous layers on anodes to use them as interlayers that prevent a direct contact of water molecules to anode particles. High-aspect ratio microbes are utilized as precursors of carbonaceous layers on TiO2 nanoparticles (m-TiO2) to enhance the conductivity and to reduce the electrolysis of WIS electrolytes. We selected the cylindrical shape of microbes that offers geometric diversity, providing us a toolkit to investigate the effect of microbe length in forming the network in binary composites and their impacts on the battery performance with WIS electrolytes. Using microbes with varying aspect ratios, the optimal microbe size to maximize the battery performance is determined. The effects of storage time on microbe size are also studied. Compared to uncoated TiO2 anodes, m-TiO2 exhibited 49% higher capacity at the 40th cycle and enhanced the cycle life close to anodes made with a conventional carbon precursor while using an 11% less amount of carbon. We performed density functional theory calculations to unravel the underlying mechanism of the performance improvement using microbe-derived carbon layers. Computational results show that high amounts of pyridinic nitrogen present in the peptide bonds in microbes are expected to slow down the water diffusion. Our findings provide key insights into the design of an interlayer for WIS anodes and open an avenue to fabricate energy storage materials using biomaterials.
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We use suspended graphene electromechanical resonators to study the variation of resonant frequency as a function of temperature. Measuring the change in frequency resulting from a change in tension, from 300 to 30 K, allows us to extract information about the thermal expansion of monolayer graphene as a function of temperature, which is critical for strain engineering applications. We find that thermal expansion of graphene is negative for all temperatures between 300 and 30 K. We also study the dispersion, the variation of resonant frequency with DC gate voltage, of the electromechanical modes and find considerable tunability of resonant frequency, desirable for applications like mass sensing and RF signal processing at room temperature. With a lowering of temperature, we find that the positively dispersing electromechanical modes evolve into negatively dispersing ones. We quantitatively explain this crossover and discuss optimal electromechanical properties that are desirable for temperature-compensated sensors.
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Grafite/química , Sistemas Microeletromecânicos/instrumentação , Nanotecnologia/instrumentação , Transdutores , Desenho de Equipamento , Análise de Falha de Equipamento , Temperatura , Condutividade TérmicaRESUMO
We report Raman and photoluminescence spectra of mono- and few-layer WSe2 and MoSe2 taken before and after exposure to a remote oxygen plasma. For bilayer and trilayer WSe2, we observe an increase in the photoluminescence intensity and a blue shift of the photoluminescence peak positions after oxygen plasma treatment. The photoluminescence spectra of trilayer WSe2 exhibit features of a bilayer after oxygen plasma treatment. Bilayer WSe2 exhibits features of a monolayer, and the photoluminescence of monolayer WSe2 is completely absent after the oxygen plasma treatment. These changes are observed consistently in more than 20 flakes. The mechanism of the changes observed in the photoluminescence spectra of WSe2 is due to the selective oxidation of the topmost layer. As a result, N-layer WSe2 is reduced to N-1 layers. Raman spectra and AFM images taken from the WSe2 flakes before and after the oxygen treatment corroborate these findings. Because of the low kinetic energy of the oxygen radicals in the remote oxygen plasma, the oxidation is self-limiting. By varying the process duration from 1 to 10 min, we confirmed that the oxidation will only affect the topmost layer of the WSe2 flakes. X-ray photoelectron spectroscopy shows that the surface layer WOx of the sample can be removed by a quick dip in KOH solution. Therefore, this technique provides a promising way of controlling the thickness of WSe2 layer by layer.
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Modern microelectronic devices have nanoscale features that dissipate power nonuniformly, but fundamental physical limits frustrate efforts to detect the resulting temperature gradients. Contact thermometers disturb the temperature of a small system, while radiation thermometers struggle to beat the diffraction limit. Exploiting the same physics as Fahrenheit's glass-bulb thermometer, we mapped the thermal expansion of Joule-heated, 80-nanometer-thick aluminum wires by precisely measuring changes in density. With a scanning transmission electron microscope and electron energy loss spectroscopy, we quantified the local density via the energy of aluminum's bulk plasmon. Rescaling density to temperature yields maps with a statistical precision of 3 kelvin/hertz(-1/2), an accuracy of 10%, and nanometer-scale resolution. Many common metals and semiconductors have sufficiently sharp plasmon resonances to serve as their own thermometers.
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Heterostructure devices with specific and extraordinary properties can be fabricated by stacking two-dimensional crystals. Cleanliness at the inter-crystal interfaces within a heterostructure is crucial for maximizing device performance. However, because these interfaces are buried, characterizing their impact on device function is challenging. Here, we show that electron-beam induced current (EBIC) mapping can be used to image interfacial contamination and to characterize the quality of buried heterostructure interfaces with nanometer-scale spatial resolution. We applied EBIC and photocurrent imaging to map photo-sensitive graphene-MoS2 heterostructures. The EBIC maps, together with concurrently acquired scanning transmission electron microscopy images, reveal how a device's photocurrent collection efficiency is adversely affected by nanoscale debris invisible to optical-resolution photocurrent mapping.
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We report a robust method for engineering the optoelectronic properties of many-layer MoS2 using low-energy oxygen plasma treatment. Gas phase treatment of MoS2 with oxygen radicals generated in an upstream N2 -O2 plasma is shown to enhance the photoluminescence (PL) of many-layer, mechanically exfoliated MoS2 flakes by up to 20 times, without reducing the layer thickness of the material. A blueshift in the PL spectra and narrowing of linewidth are consistent with a transition of MoS2 from indirect to direct bandgap material. Atomic force microscopy and Raman spectra reveal that the flake thickness actually increases as a result of the plasma treatment, indicating an increase in the interlayer separation in MoS2 . Ab initio calculations reveal that the increased interlayer separation is sufficient to decouple the electronic states in individual layers, leading to a transition from an indirect to direct gap semiconductor. With optimized plasma treatment parameters, we observed enhanced PL signals for 32 out of 35 many-layer MoS2 flakes (2-15 layers) tested, indicating that this method is robust and scalable. Monolayer MoS2 , while direct bandgap, has a small optical density, which limits its potential use in practical devices. The results presented here provide a material with the direct bandgap of monolayer MoS2 , without reducing sample thickness, and hence optical density.