RESUMO
Electrical resistivity is the key parameter in the active regions of many current nanoscale devices, from memristors to resistive random-access memory and phase-change memories. The local resistivity of the materials is engineered on the nanoscale to fit the performance requirements. Phase-change memories, for example, rely on materials whose electrical resistance increases dramatically with a change from a crystalline to an amorphous phase. Electrical characterization methods have been developed to measure the response of individual devices, but they cannot map the local resistance across the active area. Here, we propose a method based on operando electron holography to determine the local resistance within working devices. Upon switching the device, we show that electrical resistance is inhomogeneous on the scale of only a few nanometers.
RESUMO
Here we use off-axis electron holography combined with advanced transmission electron microscopy techniques to understand the opto-electronic properties of AlGaN tunnel junction (TJ)-light-emitting diode (LED) devices for ultraviolet emission. Four identical AlGaN LED devices emitting at 290 nm have been grown by metal-organic chemical vapour deposition. Then Ge doped n-type regions with and without InGaN or GaN interlayers (IL) have been grown by molecular beam epitaxy onto the top Mg doped p-type layer to form a TJ and hence a high quality ohmic metal contact. Off-axis electron holography has then been used to demonstrate a reduction in the width of the TJ from 9.5 to 4.1 nm when an InGaN IL is used. As such we demonstrate that off-axis electron holography can be used to reproducibly measure nm-scale changes in electrostatic potential in highly defected and challenging materials such as AlGaN and that systematic studies of devices can be performed. The LED devices are then characterized using standard opto-electric techniques and the improvements in the performance of the LEDs are correlated with the electron holography results.
RESUMO
Imaging of proteins at the single-molecule level can reveal conformational variability, which is essential for the understanding of biomolecules. To this end, a biologically relevant state of the sample must be retained during both sample preparation and imaging. Native electrospray ionization (ESI) can transfer even the largest protein complexes into the gas phase while preserving their stoichiometry and overall shape. High-resolution imaging of protein structures following native ESI is thus of fundamental interest for establishing the relation between gas phase and solution structure. Taking advantage of low-energy electron holography's (LEEH) unique capability of imaging individual proteins with subnanometer resolution, we investigate the conformational flexibility of Herceptin, a monoclonal IgG antibody, deposited by native electrospray mass-selected ion beam deposition (ES-IBD) on graphene. Images reconstructed from holograms reveal a large variety of conformers. Some of these conformations can be mapped to the crystallographic structure of IgG, while others suggest that a compact, gas-phase-related conformation, adopted by the molecules during ES-IBD, is retained. We can steer the ratio of those two types of conformations by changing the landing energy of the protein on the single-layer graphene surface. Overall, we show that LEEH can elucidate the conformational heterogeneity of inherently flexible proteins, exemplified here by IgG antibodies, and thereby distinguish gas-phase collapse from rearrangement on surfaces.
Assuntos
Holografia/métodos , Imunoglobulina G/química , Imagem Individual de Molécula/métodos , Conformação Proteica , Espectrometria de Massas por Ionização por ElectrosprayRESUMO
The operation of nanoscale electronic devices is related intimately to the three-dimensional (3D) charge density distributions within them. Here, we demonstrate the quantitative 3D mapping of the charge density and long-range electric field associated with an electrically biased carbon fiber nanotip with a spatial resolution of approximately 5 nm using electron holographic tomography in the transmission electron microscope combined with model-based iterative reconstruction. The approach presented here can be applied to a wide range of other nanoscale materials and devices.
RESUMO
Target skyrmion, characterized by a central skyrmion surrounded by a series of concentric cylinder domains known as kπ-skyrmions (k ≥ 2), holds promise as a novel storage state in next-generation memories. However, target skyrmions comprising one or more concentric cylindrical domains have not been observed in chiral magnets, particularly at room temperature. In this study, we experimentally achieved kπ-skyrmions (k = 2, 3, and 4) with diameters of â¼220, 320, and 410 nm, respectively, and room-temperature stability under zero magnetic field by tightly confining these topological spin textures in ß-Mn-type Co8Zn10Mn2 nanodisks. The magnetic configurations and their field-driven evolutions were simultaneously investigated by using in situ off-axis electron holography. In combination with numerical simulations, we further investigated the dependence of kmax on the nanodisk diameter. These findings highlight the potential of kπ-skyrmions as information carriers and offer insights into manipulation of kπ-skyrmions in the future.
RESUMO
Structural engineering via the template method is efficient for micro-nano assembling. However, only structural design and lack of composition control restrict their advanced application. To overcome this issue, applying a template to simultaneously realize the structural design and fine component control is highly desired, which has been ignored. In this study, a spinel-shaped MoS2 heterostructure with controlled phase ratios of 1H and 2H phase is developed using the AlOOH template method. This work demonstrates that the MoS2 phase transition mechanism from 2H to 1T is substantially attributed to the close exposed crystal's surface and approximately accordant surface energy. The superiority and additional proof are provided based on density-functional theory simulation, transmission electron microscope holography, etc. With an effective absorptance region of 6.3 GHz under a thickness of 1.4 mm, the reported samples present outstanding microwave absorption capacity. This is attributed to the beneficial coupled effect between the well-designed structure and phase regulation. This work offers valuable insights into structural engineering and component regulation template methods.
RESUMO
Although assembled hollow architectures have received considerable attention as lightweight functional materials, their uncontrollable self-aggregation and tedious synthetic methods hinder precise construction and modulation. Therefore, this study proposes a bi-ion synergistic regulation strategy to design assembled hollow-shaped cobalt spinel oxide microspheres. Dominated by the coordination-etching effects of F- and the hydrolysis-complex contributions of NH4 + , the unique construction is formed attributed to the dynamic cycles between metal complexes and precipitates. Meanwhile, their basic structures are perfectly retained after reduction treatment, enabling FeCo/CoFe2 O4 bimagnetic system to be obtained. Subsequently, in-depth analyses are conducted. Investigations reveal that multiscale magnetic coupling networks and enriched air-material heterointerfaces contribute to the remarkable magnetic-dielectric behavior, supported by the advanced off-axis electron holography technique. Consequently, the obtained FeCo/CoFe2 O4 composites exhibit excellent microwave absorption performances with minimal reflection losses (RLmin ) as high as -51.6 dB, an effective absorption bandwidth (EAB) of 4.7 GHz, and a matched thickness of 1.4 mm. Thus, this work provides an informative guide for rationally assembling building blocks into hollow architectures as advanced microwave absorbers through bi-ion and even multi-ion synergistic engineering mechanisms.
RESUMO
We measure the mean inner potential (MIP) of hematite, α-Fe2O3, using electron holography and transmission electron microscopy. Since the MIP is sensitive to valence electrons, we propose its use as a chemical bonding parameter for solids. Hematite can test the sensitivity of the MIP as a bonding parameter because of the Morin magnetic phase transition. Across this transition temperature, no change in the corundum crystal structure can be distinguished, while a change in hybridized Fe-3d and O-2p states was reported, affecting ionic bonding. For a given crystallographic phase, the change in the MIP with temperature is expected to be minor due to thermal expansion. Indeed, we measure the temperature dependence in corundum α-Al2O3(112¯0) between 95 and 295 K showing a constant MIP value of â¼16.8 V within the measurement accuracy of 0.45 V. Thus, our objectives are as follows: measure the MIP of hematite as a function of temperature and examine the sensitivity of the MIP as a bonding parameter for crystals. Measured MIPs of α-Fe2O3(112¯0) above the Morin transition are equal, 17.85 ± 0.50 V, 17.93 ± 0.50 V, at 295 K, 230 K, respectively. Below the Morin transition, at 95 K, a significant reduction of â¼1.3 V is measured to 16.56 ± 0.46 V. We show that this reduction follows charge redistribution resulting in increased ionic bonding.
RESUMO
Metal oxide nanoparticles exhibit outstanding catalytic properties, believed to be related to the presence of oxygen vacancies at the particle's surface. However, little quantitative information is known about concentrations of point defects inside and at surfaces of these nanoparticles, due to the challenges in achieving an atomically resolved experimental access. By employing off-axis electron holography, we demonstrate, using MgO nanoparticles as an example, a methodology that discriminates between mobile charge induced by electron beam irradiation and immobile charge associated with deep traps induced by point defects as well as distinguishes between bulk and surface point defects. Counting the immobile charge provides a quantification of the concentration of F2+ centers induced by oxygen vacancies at the MgO nanocube surfaces.
Assuntos
Holografia , Nanopartículas Metálicas , Elétrons , Holografia/métodos , Óxido de Magnésio , Óxidos , OxigênioRESUMO
Perpendicular shape anisotropy (PSA) offers a practical solution to downscale spin-transfer torque magnetoresistive random-access memory (STT-MRAM) beyond the sub-20 nm technology node while retaining thermal stability. However, our understanding of the thermomagnetic behavior of PSA-STT-MRAM is often indirect, relying on magnetoresistance measurements and micromagnetic modeling. Here, the magnetism of a NiFe PSA-STT-MRAM nanopillar is investigated using off-axis electron holography, providing spatially resolved magnetic information as a function of temperature. Magnetic induction maps reveal the micromagnetic configuration of the NiFe storage layer (â¼60 nm high, ≤20 nm diameter), confirming the PSA induced by its 3:1 aspect ratio. In situ heating demonstrates that the PSA of the storage layer is maintained up to at least 250 °C, and direct quantitative measurements reveal a moderate decrease of magnetic induction. Hence, this study shows explicitly that PSA provides significant stability in STT-MRAM applications that require reliable performance over a range of operating temperatures.
RESUMO
Off-axis electron holography was used to reveal remote doping in GaAs nanowires occurring duringin situannealing in a transmission electron microscope. Dynamic changes to the electrostatic potential caused by carbon dopant diffusion upon annealing were measured across GaAs nanowires with radial p-p+ core-shell junctions. Electrostatic potential profiles were extracted from holographic phase maps and built-in potentials (Vbi) and depletion layer widths (DLWs) were estimated as function of temperature over 300-873 K. Simulations in absence of remote doping predict a significant increase ofVbiand DLWs with temperature. In contrast, we measured experimentally a nearly constantVbiand a weak increase of DLWs. Moreover, we observed the appearance of a depression in the potential profile of the core upon annealing. We attribute these deviations from the predicted behavior to carbon diffusion from the shell to the core through the nanowire sidewalls, i.e. to remote doping, becoming significant at 673 K. The DLW in the p and p+ regions are in the 10-30 nm range.
RESUMO
Single crystalline magnetic FeCo nanostars were prepared using an organometallic approach under mild conditions. The fine-tuning of the experimental conditions allowed the direct synthesis of these nano-octopods with body-centered cubic (bcc) structure through a one-pot reaction, contrarily to the seed-mediated growth classically used. The FeCo nanostars consist of 8 tetrahedrons exposing {311} facets, as revealed by high resolution transmission electron microscopy (HRTEM) imaging and electron tomography (ET), and exhibit a high magnetization comparable with the bulk one (Ms = 235 A·m2·kg-1). Complex 3D spin configurations resulting from the competition between dipolar and exchange interactions are revealed by electron holography. This spin structures are stabilized by the high aspect ratio tetrahedral branches of the nanostars, as confirmed by micromagnetic simulations. This illustrates how magnetic properties can be significantly tuned by nanoscale shape control.
RESUMO
The design and fabrication of transition metal dichalcogenides (TMDs) are of paramount significance for water-splitting process. However, the limited active sites and restricted conductivity prevent their further application. Herein, a polarization boosted strategy is put forward for the modification of TMDs to promote the absorption of the intermediates, leading to the improved catalytic performance. By the forced assembly of TMDs (WS2 as the example) and carbon nanotubes (CNTs) via spray-drying method, such frameworks can remarkably achieve low overpotentials and superior durability in alkaline media, which is superior to most of the TMDs-based catalysts. The two-electrode cell for water-splitting also exhibits perfect activity and stability. The enhanced catalytic performance of WS2 /CNTs composite is mainly owing to the strong polarized coupling between CNTs and WS2 nanosheets, which significantly promotes the charge redistribution on the interface of CNTs and WS2 . Density functional theory (DFT) calculations show that the CNTs enrich the electron content of WS2 , which favors electron transportation and accelerates the catalysis. Moreover, the size of WS2 is restricted caused by the confinement of CNTs, leading to the increased numbers of active sites, further improving the catalysis. This work opens a feasible route to achieve the optimized assembling of TMDs and CNTs for efficient water-splitting process.
RESUMO
While metal-based electrocatalysts have garnered extensive attention owing to the large variety of enzyme-mimic properties, the search for such highly-efficient catalysts still relies on empirical explorations, owing to the lack of predictive indicators as well as the ambiguity of structure-activity relationships. Notably, surface electronic structures play a crucial role in metal-based catalysts yet remain unexplored in enzyme-mimics. Herein, the authors investigate the electronic structure as a possible indicator of electrocatalytic activities of H2 O2 decomposition and glucose oxidation using Pd@Pt core-shell nanocrystals as a well-defined platform. The electron densities of the Pd@Pt are modulated with the correlation of strain through precise control of surface orientation and the number of atomic layers. The close relationships between the electrocatalytic activities and the surface charge accumulation are found, in which the increase of the electron accumulation can enhance both the enzyme-mimic activities. As a result, the Pd@Pt3L icosahedra with compressive strain in Pt shells exhibit the highest electrocatalytic activities for H2 O2 decomposition and glucose oxidation. Such systematic and comprehensive study provides the structure-activity relationships and paves a new way for the rational design of metal-based electrocatalysts. Especially, the charge accumulation degrees may serve as a general performance indicator for metal-based catalysts.
Assuntos
Nanopartículas , Platina , Catálise , Eletrônica , PaládioRESUMO
Achieving strong adsorption and catalytic ability toward polar lithium polysulfide species (LiPSs) of the sulfur host in lithium-sulfur (Li-S) batteries is essential for their electrochemical cyclic stability. Herein, a strategy of "self-termination of ion exchange" is put forward to synthesize the novel yolk-shell sulfur host composed of ZnO nanoparticles confined in Co-doped NiO (CDN) polyhedron (ZCCDN). After sulfur infiltration, the obtained S/ZCCDN cathode achieves excellent performance of 738.56 mAh g-1 after 500 cycles at 0.5 C with a very low capacity decay rate of only 0.048% per cycle. Even at 1 C, 501.05 mAh g-1 could be retained after 500 cycles, suggesting a capacity decay ratio of only 0.076% per cycle. The good cycle performance is attributed to the improved LiPSs' conversion kinetics, which originates from ZCCDN's sturdy chemical affinity and strong catalytic ability to polar LiPSs. For the first time, by electron holography, the local interfacial polarization electric field is clarified to be existed in the material which is conducive to the capture of LiPSs and the migration of electrons and Li+ from the mesopores. This work provides a rational way for the use of zeolitic imidazolate frameworks (ZIFs) and development of cathode materials for Li-S batteries.
RESUMO
The van der Waals heterostructures, which explore the synergetic properties of 2D materials when assembled into 3D stacks, have already brought to life a number of exciting phenomena and electronic devices. Still, the interaction between the layers in such assembly, possible surface reconstruction, and intrinsic and extrinsic defects are very difficult to characterize by any method, because of the single-atomic nature of the crystals involved. Here we present a convergent beam electron holographic technique which allows imaging of the stacking order in such heterostructures. Based on the interference of electron waves scattered on different crystals in the stack, this approach allows one to reconstruct the relative rotation, stretching, and out-of-plane corrugation of the layers with atomic precision. Being holographic in nature, our approach allows extraction of quantitative information about the 3D structure of the typical defects from a single image covering thousands of square nanometers. Furthermore, qualitative information about the defects in the stack can be extracted from the convergent diffraction patterns even without reconstruction, simply by comparing the patterns in different diffraction spots. We expect that convergent beam electron holography will be widely used to study the properties of van der Waals heterostructures.
RESUMO
Arrays of interacting 2D nanomagnets display unprecedented electromagnetic properties via collective effects, demonstrated in artificial spin ices and magnonic crystals. Progress toward 3D magnetic metamaterials is hampered by two challenges: fabricating 3D structures near intrinsic magnetic length scales (sub-100 nm) and visualizing their magnetic configurations. Here, we fabricate and measure nanoscale magnetic gyroids, periodic chiral networks comprising nanowire-like struts forming three-connected vertices. Via block copolymer templating, we produce Ni75Fe25 single-gyroid and double-gyroid (an inversion pair of single-gyroids) nanostructures with a 42 nm unit cell and 11 nm diameter struts, comparable to the exchange length in Ni-Fe. We visualize their magnetization distributions via off-axis electron holography with nanometer spatial resolution and interpret the patterns using finite-element micromagnetic simulations. Our results suggest an intricate, frustrated remanent state which is ferromagnetic but without a unique equilibrium configuration, opening new possibilities for collective phenomena in magnetism, including 3D magnonic crystals and unconventional computing.
RESUMO
Metal-organic framework (MOF) is highly desirable as a functional material owing to its low density, tunable pore size, and diversity of coordination formation, but limited by the poor dielectric properties. Herein, by controlling the solvent and mole ratio of cobalt/linker, multidimension-controllable MOF-derived nitrogen-doped carbon materials exhibit tunable morphology from sheet-, flower-, cube-, dodecahedron- to octahedron-like. Tunable electromagnetic parameters of Co@N-doped carbon composites (Co@NC) can be obtained and the initial MOF precursor determines the distribution of carbon framework and magnetic cobalt nanoparticles. Carbonized Co@NC composites possess the following advantages: i) controllable dimension and morphology to balance the electromagnetic properties with evenly charged density distribution; ii) magnetic-carbon composites offer plenty of interfacial polarization and strong magnetic coupling network; iii) a MOF-derived dielectric carbon skeleton provides electronic transportation paths and enhances conductive dissipation. Surface-mediated magnetic coupling reflects the stray magnetic flux field, which is corroborated by the off-axis electron holography and micro-magnetic simulation. Optimized octadecahedral Co@NC sample exhibits the best microwave absorption (MA) of -53.0 dB at the thickness of 1.8 mm and broad effective frequency from 11.4 to 17.6 GHz (Ku-band). These results pave the way to fabricate high-performance MA materials with balanced electromagnetic distribution and controlled morphology.
RESUMO
The growth of cobalt nanopatterns (NPs) using focused electron-beam induced deposition (FEBID) for localised magnetic studies is presented. The initial FEBID products are shown to be polycrystalline and form hetero-structured core-shell NPs through surface oxidation. Off-axis electron holography is performed to reconstruct their morphology, thickness profile and image their individual magnetic vortex domain states. In situ annealing to 400°C promoted migration of the Co-overspray to grow the Co NPs and improved their crystallinity through coarsening, as well as induced diffusion of embedded carbon out of their surface. It is found that the change in their morphology and chemical instability under heating restricts their suitability for examining thermally induced magnetic variations. LAY DESCRIPTION: In this paper, electron microscopy is used to deposit magnetic cobalt nanopatterns and characterise the effect of in-situ heating on their chemistry, structure and magnetic properties. The electron beam of the secondary electron microscope is used to dissociate an injected precursor gas near the SiN membrane substrate of in-situ transmission electron microscopy (TEM) chips and locally deposit the elemental Co in circular patterns â¼ 90 nm in diameter. TEM reveals formation of a Co-oxide shell and embedding of carbon from the precursor gas during growth. The technique of electron holography is used to image the magnetism of the core-shell Co / Co-oxide nanopatterns, which are shown to exhibit magnetic vortex states. In-situ annealing results in migration of the Co overspray to increase their height and carbon diffusion from their surface, as well as change in their original magnetic state through change of orientation. It is found that the change in the morphology and chemistry of Co nanopatterns under heating limits their use for studying the effect of temperature on their magnetism in isolation.
RESUMO
Imaging single proteins has been a long-standing ambition for advancing various fields in natural science, as for instance structural biology, biophysics, and molecular nanotechnology. In particular, revealing the distinct conformations of an individual protein is of utmost importance. Here, we show the imaging of individual proteins and protein complexes by low-energy electron holography. Samples of individual proteins and protein complexes on ultraclean freestanding graphene were prepared by soft-landing electrospray ion beam deposition, which allows chemical- and conformational-specific selection and gentle deposition. Low-energy electrons do not induce radiation damage, which enables acquiring subnanometer resolution images of individual proteins (cytochrome C and BSA) as well as of protein complexes (hemoglobin), which are not the result of an averaging process.