Silicon (Si) is broadly used in electrochemical and photoelectrochemical devices, where the capacitive and Faradaic reactions at the Si/water interfaces are critical for signal transduction or noise generation. However, probing the electrified Si/water interface at the microscopic level remains a challenging task. Here we focus on hydrogenated Si surfaces in contact with water, relevant to transient electronics and photoelectrochemical modulation of biological cells and tissues. We show that by carrying out first-principles molecular dynamics simulations of the Si(100)/water interface in the presence of an electric field we can realistically correlate the computed flat-band potential and tunneling current images at the interface with experimentally measured capacitive and Faradaic currents. Specifically, we validate our simulations in the presence of bias by performing pulsed chronoamperometry measurements on Si wafers in solution. Consistent with prior experiments, our measurements and simulations indicate the presence of voltage-dependent capacitive currents at the interface. We also find that Faradaic currents are weakly dependent on the applied bias, which we relate to surface defects present in newly prepared samples.
more »
« less
Dynamical nonlinear memory capacitance in biomimetic membranes
Abstract Two-terminal memory elements, or memelements, capable of co-locating signal processing and memory via history-dependent reconfigurability at the nanoscale are vital for next-generation computing materials striving to match the brain’s efficiency and flexible cognitive capabilities. While memory resistors, or memristors, have been widely reported, other types of memelements remain underexplored or undiscovered. Here we report the first example of a volatile, voltage-controlled memcapacitor in which capacitive memory arises from reversible and hysteretic geometrical changes in a lipid bilayer that mimics the composition and structure of biomembranes. We demonstrate that the nonlinear dynamics and memory are governed by two implicitly-coupled, voltage-dependent state variables—membrane radius and thickness. Further, our system is capable of tuneable signal processing and learning via synapse-like, short-term capacitive plasticity. These findings will accelerate the development of low-energy, biomolecular neuromorphic memelements, which, in turn, could also serve as models to study capacitive memory and signal processing in neuronal membranes.
more »
« less
- Award ID(s):
- 1631472
- PAR ID:
- 10153930
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 10
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
We introduce a capacitive MEMS filter that uses electrostatic levitation for actuation and sensing. The advantage of this electrode configuration is that it does not suffer from the pull-in instability and therefore tremendously high voltages can be applied to this system. A large sensing voltage will produce a large output signal, which boosts the signal to noise ratio. The filter outputs about a 110mV peak-to-peak signal when operated at 175V, and can be boosted to 175mV by increasing the voltage to 250V. Because pull-in is eliminated, voltages much higher than 250V can be applied. An outline of the filter design and operating principle is discussed. A model of the filter is derived and analyzed to show the mechanical response and approximate peak-to-peak signal output. This study shows the feasibility of a capacitive sensor that is based on electrostatic levitation, and outlines the advantages it has over traditional parallel-plate electrode configurations. This design is promising for signal signal processing applications where large strokes are important.more » « less
-
Abstract Brain‐inspired (or neuromorphic) computing circumvents costly bottlenecks in conventional Von Neumann architectures by collocating memory and processing. This is accomplished through dynamic material architectures, strengthening or weakening internal conduction pathways similar to synaptic connections within the brain. A new class of neuromorphic materials approximates synaptic interfaces using lipid membranes assembled via the droplet interface bilayer (DIB) technique. These DIB membranes have been studied as novel memristors or memcapacitors owing to the soft, reconfigurable nature of both the lipid membrane geometry and the embedded ion‐conducting channels. In this work, a biomolecular approach to neuromorphic materials is expanded frommodel synapsesto acharge‐integrating model neuron. In these serial membrane networks, it is possible to create distributions of voltage‐sensitive gates capable of trapping ionic charge. This trapped charge creates transmembrane potential differences that drive changes in the system's net capacitance through electrowetting, providing a synaptic weight that changes in response to the history and timing of input signals. This fundamental change from interfacial memory (dimensions of the membrane) to internal memory (charge trapped within the droplets) provides a functional plasticity capable of multiple weights, longer‐term retention roughly an order of magnitude greater than memory stored in the membranes alone, and programming‐erasure.more » « less
-
Abstract Backscatter interferometry (BSI) is a refractive index (RI) detection method that is easily integrated with capillary electrophoresis (CE) and is capable of detecting species ranging from inorganic ions to proteins without additional labels or contrast agents. The BSI signal changes linearly with the square of the separation voltage which has been used to quantify sample injection, but has not been explored as a potential signal enhancement mechanism in CE. Here we develop a mathematical model that predicts a signal enhancement at high field strengths, where the BSI signal is dominated by the voltage dependent mechanism. This is confirmed in both simulation and experiment, which show that the analyte peak area grows linearly with separation voltage at high field strengths. This effect can be exploited by adjusting the background electrolyte (BGE) to increase the conductivity difference between the BGE and analyte zones, which is shown to improve BSI performance. We also show that this approach has utility in small bore capillaries where larger separation fields can be applied before excess Joule heating degrades the separation. Unlike other optical detection methods that generally degrade as the optical pathlength is reduced, the BSI signal-to-noise can improve in small bore capillaries as the larger separation fields enhance the signal.more » « less
-
Phospholipid bilayers can be described as capacitors whose capacitance per unit area (specific capacitance, Cm) is determined by their thickness and dielectric constant–independent of applied voltage. It is also widely assumed that the Cm of membranes can be treated as a “biological constant”. Recently, using droplet interface bilayers (DIBs), it was shown that zwitterionic phosphatidylcholine (PC) lipid bilayers can act as voltage-dependent, nonlinear memory capacitors, or memcapacitors. When exposed to an electrical “training” stimulation protocol, capacitive energy storage in lipid membranes was enhanced in the form of long-term potentiation (LTP), which enables biological learning and long-term memory. LTP was the result of membrane restructuring and the progressive asymmetric distribution of ions across the lipid bilayer during training, which is analogous, for example, to exponential capacitive energy harvesting from self-powered nanogenerators. Here, we describe how LTP could be produced from a membrane that is continuously pumped into a nonequilibrium steady state, altering its dielectric properties. During this time, the membrane undergoes static and dynamic changes that are fed back to the system’s potential energy, ultimately resulting in a membrane whose modified molecular structure supports long-term memory storage and LTP. Here, we also show that LTP is very sensitive to different salts (KCl, NaCl, LiCl, and TmCl3), with LiCl and TmCl3 having the most profound effect in depressing LTP, relative to KCl. This effect is related to how the different cations interact with the bilayer zwitterionic PC lipid headgroups primarily through electric-field-induced changes to the statistically averaged orientations of water dipoles at the bilayer headgroup interface.more » « less
An official website of the United States government
