Isolated, atomically thin conducting membranes of graphite, called graphene, have recently been the subject of intense research with the hope that practical applications in fields ranging from electronics to energy science will emerge1. Here, we show that when immersed in ionic solution, a layer of graphene becomes a new electrochemical structure we call a trans-electrode. The trans-electrode's unique properties are the consequence of the atomic scale proximity of its two opposing liquid-solid interfaces together with graphene's well known in-plane conductivity. We show that several trans-electrode properties are revealed by ionic conductance measurements on a CVD grown graphene membrane that separates two aqueous ionic solutions. Although our membranes are only one to two atomic layers2,3 thick, we find they are remarkable ionic insulators with a very small stable conductance that depends on the ion species in solution. Electrical measurements on graphene membranes in which a single nanopore has been drilled show that the membrane's effective insulating thickness is less than one nanometer. This small effective thickness makes graphene an ideal substrate for very high-resolution, high throughput nanopore-based single molecule detectors. The sensitivity of graphene's in-plane electronic conductivity to its immediate surface environment, as influenced by trans-electrode potential, will offer new insights into atomic surface processes and sensor development opportunities.
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.
An ideal technique for observing nanoscale assembly would provide atomic-resolution images of both the products and the reactants in real time. Using a transmission electron microscope (TEM) we image in situ the electrochemical deposition of lead from an aqueous solution of lead(II) nitrate. Both the lead deposits and the local Pb2+ concentration can be visualized. Depending on the rate of potential change and the potential history, lead deposits on the cathode in a structurally compact layer or in dendrites. In both cases the deposits can be removed and the process repeated. Asperities that persist through many plating and stripping cycles consistently nucleate larger dendrites. Quantitative digital image analysis reveals excellent correlation between changes in the Pb2+ concentration, the rate of lead deposition, and the current passed by the electrochemical cell. Real-time electron microscopy of dendritic growth dynamics and the associated local ionic concentrations can provide new insight into the functional electrochemistry of batteries and related energy storage technologies.
Conductive bridge random access memory (CBRAM) is a leading candidate to supersede flash memory, but poor understanding of its switching process impedes widespread implementation. The underlying physics and basic, unresolved issues such as the connecting filament's growth direction can be revealed with direct imaging, but the nanoscale target region is completely encased and thus difficult to access with real-time, high-resolution probes. In Pt/Al2O3/Cu CBRAM devices with a realistic topology, we find that the filament grows backward toward the source metal electrode. This observation, consistent over many cycles in different devices, corroborates the standard electrochemical metallization model of CBRAM operation. Time-resolved scanning transmission electron microscopy (STEM) reveals distinct nucleation-limited and potential-limited no-growth periods occurring before and after a connection is made, respectively. The subfemtoampere ionic currents visualized move some thousands of atoms during a switch and lag the nanoampere electronic currents.
We demonstrate an ion implantation method for large-scale synthesis of high quality graphene films with controllable thickness. Thermally annealing polycrystalline nickel substrates that have been ion implanted with carbon atoms results in the surface growth of graphene films whose average thickness is controlled by implantation dose. The graphene film quality, as probed with Raman and electrical measurements, is comparable to previously reported synthesis methods. The implantation synthesis method can be generalized to a variety of metallic substrates and growth temperatures, since it does not require a decomposition of chemical precursors or a solvation of carbon into the substrate.
In standard electron beam-induced current (EBIC) imaging, the scanning electron beam creates electron-hole pairs that are separated by an in-sample electric field, producing a current in the sample. In standard scanning electron microscopy (SEM), the scanning electron beam ejects secondary electrons (SE) that are detected away from the sample. While a beam electron in a scanning transmission electron microscope (STEM) can produce many electron-hole pairs, the yield of SE is only a few percent for beam energies in the range 60-300 keV, making the latter signal much more difficult to detect on-sample as an EBIC. Here we show that the on-sample EBIC in a STEM registers both SE emission and capture as holes and electrons, respectively. Detecting both charge carriers produces differential image contrast not accessible with standard, off-sample SE imaging. In a double-EBIC imaging configuration incorporating two current amplifiers, both charge carriers can even be captured simultaneously. Compared to the currents produced in standard EBIC imaging, which only highlights the regions in a sample that contain electric fields, the EBIC produced by SE, or SEEBIC, are small (pA-scale). But SEEBIC imaging can produce contrast anywhere in a sample, exposing the texture of buried interfaces, connectivity, and other electronic properties of interest in nanoelectronic devices, even in metals and other structures without internal electric fields.
Graphene's structure bears on both the material's electronic properties and fundamental questions about long range order in two-dimensional crystals. We present an analytic calculation of selected area electron diffraction from multi-layer graphene and compare it with data from samples prepared by chemical vapor deposition and mechanical exfoliation. A single layer scatters only 0.5% of the incident electrons, so this kinematical calculation can be considered reliable for five or fewer layers. Dark-field transmission electron micrographs of multi-layer graphene illustrate how knowledge of the diffraction peak intensities can be applied for rapid mapping of thickness, stacking, and grain boundaries. The diffraction peak intensities also depend on the mean-square displacement of atoms from their ideal lattice locations, which is parameterized by a Debye-Waller factor. We measure the Debye-Waller factor of a suspended monolayer of exfoliated graphene and find a result consistent with an estimate based on the Debye model. For laboratory-scale graphene samples, finite size effects are sufficient to stabilize the graphene lattice against melting, indicating that ripples in the third dimension are not necessary.
In order to test recently predicted ballistic nanofriction (ultra-low drag and enhanced lubricity) of gold nanocrystals on graphite at high surface speeds, we use the quartz microbalance technique to measure the impact of deposition of gold nanocrystals on graphene. We analyze our measurements of changes in frequency and dissipation induced by nanocrystals using a framework developed for friction of adatoms on various surfaces. We find the lubricity of gold nanocrystals on graphene to be even higher than that predicted for the ballistic nanofriction, confirming the enhanced lubricity predicted at high surface speeds. Our complementary molecular dynamics simulations indicate that such high lubricity is due to the interaction strength between gold nanocrystals and graphene being lower than previously assumed for gold nanocrystals and graphite.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.