Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “RECTIFICATION”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14

Effect of the Electric Double Layer on the Activation Energy of Ion Transport in Conical Nanopores

Measured apparent activation energies, $E_A$, of ion transport (K + and Cl – ) in conical glass nanopores are reported as a function of applied voltage (-0.5 to 0.5 V), pore size (20–2000 nm), and electrolyte concentration (0.1–50 mM). $E_A$ values for transport within an electrically charged conical glass nanopore differ from the bulk values due to the voltage and temperature-dependent distribution of the ions within the double layer. Remarkably, nanopores that display ion current rectification also display a large decrease in $E_A$ under accumulation mode conditions (at applied negative voltages versus an external ground) and a large increase in $E_A$ under depletion mode conditions (at positive voltages). Finite element simulations based on the Poisson–Nernst–Planck model semiquantitatively predict the measured temperature-dependent conductivity and dependence of $E_A$ on applied voltage. The results highlight the relationships between the distribution of ions with the nanopore, ionic current, and $E_A$ and their dependencies on pore size, temperature, ion concentration, and applied voltage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Junctions: Control of the Energy Gap Achieved by a Pinning Effect

Single-molecule junctions are the constitutive components of molecular electronics circuits. For any potential application, the energy gap in the junction, i.e., the accumulated energy difference between the electrode Fermi level and the two frontier energy levels of the molecule, is a key property. In this study, using the nonequilibrium Green’s function coupled to the density functional theory framework (NEGF-DFT) method, we show that the gap of the molecule inserted between electrodes can differ largely from the gap of the same molecule, at the isolated level. It can be widely compressed by tuning the alignment mechanism at each metal/molecule interface. In the context of molecular rectification, we show that this mechanism relates to the pinning effect. We discuss the different parameters affecting the compression of the gap and its efficiency. Interestingly, we find that the structure both of the molecule and of the anchoring group plays an important role. Finally, we investigate the evolution of these features out-of-equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Concentration-Polarization-Induced Precipitation and Ionic Current Oscillations with Tunable Frequency

At the nanoscale, charges present at the surfaces of liquid–solid interfaces greatly influence the properties of ions and molecules present in the solution, and can lead to nanoscale effects such as ion selectivity, ion current rectification, and modulation of local ionic concentrations. Concentration polarization is another nanoscale phenomenon whereby ion concentrations are enriched at one opening of an ion-selective nanopore and depleted at the other. We demonstrate that when a nanopore is in contact with a weakly soluble salt present at a concentration below its solubility product, concentration polarization can lead to locally enhanced ionic concentrations and precipitation of the salt. Formed precipitates partially or fully occlude the nanopore’s opening as indicated by a measured transient decrease of the nanopore’s conductance. We have confirmed experimental conditions at which the locally created precipitate is either pushed through or dissolved, clearing the pore entrance and allowing the precipitation reaction to occur again. The dynamic process of precipitate formation and dissolution is observed as ion current fluctuations and oscillations with frequencies reaching 200 Hz. The frequency of the system operation exceeds other nanopore-based oscillators by 2 orders of magnitude, which we believe stems from the 30 nm length of the pores examined here, versus ~10 μm long pores reported before.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tip-Enhanced Raman Nanospectroscopy of Smooth Spherical Gold Nanoparticles

We record nanoscale-resolved chemical images of thiobenzonitrile (TBN)-functionalized smooth gold nanospheres on silicon via tip-enhanced Raman (TER) nano-spectroscopy. The recorded images trace the nascence of the familiar doughnut-shaped scattering profile of nanoparticles on silicon at its origin (the particle surface), which appears as a horseshoe-shaped scattering pattern under our experimental conditions. The local optical field maps are in agreement with their simulated finite-difference time-domain analogues. Analysis of the recorded spectra with the aid of ab initio molecular dynamics-based Raman spectral simulations further suggests that optical rectification and molecular charging take place throughout the course of atomic force microscopy-based TER nanoscale chemical imaging.

Bhattarai, Ashish↗

A Closer Look at Corrugated Au Tips

A series of optical and electron microscopies are utilized in concert to unravel the structural, optical, and plasmonic properties of corrugated metallic tips. While the overall microscopic shapes of the tips dictate their optical resonances and plasmonic field enhancement factors, nanometric structural details govern their tip-enhanced Raman (TER) spectra and images. Using 4-thiobenzonitrile (TBN) as a molecular reporter, spatially resolved TER spectra reveal that optical rectification and molecular charging are among the prominent observables in the tip-tip TER geometry. The comparisons we provide reinforce the complexity of what otherwise may be regarded as sharp tip probes. We show the spurious appearance of anions is driven by highly localized resonances that appear as a result of surface corrugation and their manifestation throughout the course of TER nano-spectroscopy complicates spectral assignments, particularly in works aimed at understanding plasmon-enhanced/induced chemical transformations through enhanced Raman spectroscopy and imaging. Overall, nanoscale spatial variations in the TERS spectra suggest that the tip-tip geometry sustains junction plasmons that appear very different from what may be expected from the hybridization of the bulk tip resonances.

Bhattarai, Ashish↗

Crucial role of nuclear dynamics for electron injection in a dye–semiconductor complex

In this study, we investigate the electron injection from a terrylene-based chromophore to the TiO 2 semiconductor bridged by a recently proposed phenyl-amide-phenyl molecular rectifier. The mechanism of electron transfer is studied by means of quantum dynamics simulations using an extended Hückel Hamiltonian. It is found that the inclusion of the nuclear motion is necessary to observe the photoinduced electron transfer. In particular, the fluctuations of the dihedral angle between the terrylene and the phenyl ring modulate the localization and thus the electronic coupling between the donor and acceptor states involved in the injection process. The electron propagation shows characteristic oscillatory features that correlate with interatomic distance fluctuations in the bridge, which are associated with the vibrational modes driving the process. The understanding of such effects is important for the design of functional dyes with optimal injection and rectification properties.

36 MATERIALS SCIENCE↗

Gate-Tunable Semiconductor Heterojunctions from 2D/3D van der Waals Interfaces

Van der Waals (vdW) semiconductors are attractive for highly scaled devices and heterogeneous integration since they can be isolated into self-passivated, two-dimensional (2D) layers that enable superior electrostatic control. These attributes have led to numerous demonstrations of field-effect devices ranging from transistors to triodes. By exploiting the controlled, substitutional doping schemes in covalently-bonded, three-dimensional (3D) semiconductors and the passivated surfaces of 2D semiconductors, one can construct devices that can exceed performance metrics of “all-2D” vdW heterojunctions. Here, we demonstrate, 2D/3D semiconductor heterojunctions using MoS2 as the prototypical 2D semiconductor laid upon Si and GaN as the 3D semiconductor layers. By tuning the Fermi levels in MoS2, we demonstrate devices that concurrently exhibit over seven orders of magnitude modulation in rectification ratios and conductance. Our results further suggest that the interface quality does not necessarily affect Fermi-level tuning at the junction opening up possibilities for novel 2D/3D heterojunction device architectures

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Dislocation-Assisted Quasi-Two-Dimensional Semiconducting Nanochannels Embedded in Perovskite Thin Films

Defect engineering in perovskite thin films has attracted extensive attention recently due to the films’ atomic-scale modification, allowing for remarkable flexibility to design novel nanostructures for next generation nanodevices. However, the defect-assisted three-dimensional nanostructures in thin film matrices usually has large misfit strain and thus causes unstable thin film structures. In contrast, defect-assisted one- or two-dimensional nanostructures embedded in thin films can sustain large misfit strains without relaxation, which make them suitable for defect engineering in perovskite thin films. Here, we reported the fabrication and characterization of edge-type misfit dislocation-assisted two-dimensional BiMnO x nanochannels embedded in SrTiO 3 /La 0.7 Sr 0.3 MnO 3 /TbScO 3 perovskite thin films. The nanochannels are epitaxially grown from the surrounding films without noticeable misfit strain. Diode-like current rectification was spatially observed at nanochannels due to the formation of Schottky junctions between BiMnO x nanochannels and conducting La 0.7 Sr 0.3 MnO 3 thin films. Such atomically scaled heterostructures constitute more flexible ultimate functional units for nanoscale electronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Deriving Material Properties from Feedback Error Signals in Scanning Tunneling Microscopy

Imperfections in measurements, e.g., deviations and broadening, are not devoid of information; rather, they can reveal valuable physical properties and processes. Scanning tunneling microscopy leverages a negative feedback loop to regulate the tunneling current. Practically, current fluctuates around its set point, and such deviations are considered insignificant and ignored. Here, in this study, we investigate the information embedded in these deviations. In the constant-current mode with an active feedback loop, we observe an unexpected persistent DC current offset from its set point when the tunneling junction is periodically perturbed. We demonstrate both experimentally and theoretically that such error signals encode local tunneling barrier heights and the square of local differential conductance as a consequence of the interplay between rectification and active feedback compensation. We provide evidence on the generalizability of this phenomenology to other negative feedback systems. This new approach has the potential to broadly impact physical sciences by allowing rapid measurements without lock-in amplifiers.

36 MATERIALS SCIENCE↗

Two-step growth of two-dimensional WSe 2 /MoSe 2 heterostructures

Two dimensional (2D) materials have attracted great attention due to their unique properties and atomic thickness. Although various 2D materials have been successfully synthesized with different optical and electrical properties, a strategy for fabricating 2D heterostructures must be developed in order to construct more complicated devices for practical applications. Here we demonstrate for the first time a two-step chemical vapor deposition (CVD) method for growing transition-metal dichalcogenide (TMD) heterostructures, where MoSe 2 was synthesized first and followed by an epitaxial growth of WSe 2 on the edge and on the top surface of MoSe 2 . Compared to previously reported one-step growth methods, this two-step growth has the capability of spatial and size control of each 2D component, leading to much larger (up to 169 μm) heterostructure size, and cross-contamination can be effectively minimized. Furthermore, this two-step growth produces well-defined 2H and 3R stacking in the WSe 2 /MoSe 2 bilayer regions and much sharper in-plane interfaces than the previously reported MoSe 2 /WSe 2 heterojunctions obtained from one-step growth methods. The resultant heterostructures with WSe 2 /MoSe 2 bilayer and the exposed MoSe 2 monolayer display rectification characteristics of a p-n junction, as revealed by optoelectronic tests, and an internal quantum efficiency of 91% when functioning as a photodetector. As a result, a photovoltaic effect without any external gates was observed, showing incident photon to converted electron (IPCE) efficiencies of approximately 0.12%, providing application potential in electronics and energy harvesting.

2D heterostructures↗

KTaO 3 -Based Supercurrent Diode

The supercurrent diode effect (SDE), characterized by nonreciprocal critical currents, represents a promising building block for future dissipationless electronics and quantum circuits. Realizing SDE requires breaking both time-reversal and inversion symmetry in the device. Here we use conductive atomic force microscope (c-AFM) lithography to pattern reconfigurable superconducting weak links (WLs) at the LaAlO 3 /KTaO 3 (LAO/KTO) interface. By deliberately engineering the WL geometry at the nanoscale, we realize SDE in these devices in the presence of modest out-of-plane magnetic fields. The SDE polarity can be reversed by simply changing the WL position, and the rectification efficiency reaches up to 13% under optimal magnetic field conditions. Time-dependent Ginzburg–Landau simulations reveal that the observed SDE originates from asymmetric vortex motion in the inversion-symmetry-breaking device geometry. This demonstration of SDE in the LAO/KTO system establishes a versatile platform for investigating and engineering vortex dynamics, forming the basis for engineered quantum circuit elements.

C-AFM lithography↗

Introduction of Interfacial Charges to Black Phosphorus for a Family of Planar Devices

The capabilities to tune the conduction properties of materials by doping or electric fields are essential for the design of electronic devices. However, in two-dimensional materials substitutional doping has been achieved in only a few systems, such as Nb substitutional doping in MoS 2 . Surface charge transfer is still one of the popular ways to control whether the conduction is dominated by holes or electrons. Here, we demonstrate that a capping layer of cross-linked poly(methyl methacrylate) modifies the potential in a black phosphorus (BP) layer so that conduction in the absence of an external electric field is dominated by electrons, rather than holes. Using this technique to form adjoining regions dominated by hole and electron conduction, a family of novel planar devices, such as BP-gated diodes, BP bidirectional rectifier, and BP logic inverters, can be fabricated. The devices are potentially useful for electronic applications, including rectification and switching.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Electronic Structure and Band Alignment at the NiO and SrTiO 3 p–n Heterojunctions

Understanding the energetics at the interface including the alignment of valence and conduction bands, built-in potentials, and ionic and electronic reconstructions, is an important challenge in designing oxide interfaces that have controllable multi-functionalities for novel (opto-)electronic devices. In this work, we report detailed investigations on the hetero-interface of wide bandgap p-type NiO and n-type SrTiO3 (STO). We show that despite a large lattice mismatch (~7%) and dissimilar crystal structure, high-quality NiO and Li doped NiO (LNO) thin films can be epitaxially grown on STO(001) substrates through a domain matching epitaxy (DME) mechanism. X-ray photoelectron spectroscopy (XPS) studies indicate that NiO/STO heterojunctions form a type II “staggered” band alignment. In addition, a large built-in potential of up to 0.97 eV was observed at the interface of LNO and Nb doped STO (NbSTO). The LNO/NbSTO p-n heterojunctions exhibit a large rectification ratio of 2×103, but also a large ideality factor of 4.3. The NiO/STO p-n heterojunctions have important implication for applications in photocatalysis and photodetector as the interface provides favourable energetics for facile separation and transport of photogenerated electrons and holes.

36 MATERIALS SCIENCE↗

Visible-Blind UV Photodetector Based on Single-Walled Carbon Nanotube Thin Film/ZnO Vertical Heterostructures

Ultraviolet (UV) photodetectors based on heterojunctions of conventional (Ge, Si, and GaAs) and wide bandgap semiconductors have been recently demonstrated, but achieving high UV sensitivity and visible-blind photodetection still remains a challenge. Here in this work, we utilized a semitransparent film of p-type semiconducting single-walled carbon nanotubes (SC-SWNTs) with an energy gap of 0.68 ± 0.07 eV in combination with a molecular beam epitaxy grown n-ZnO layer to build a vertical p-SC-SWNT/n-ZnO heterojunction-based UV photodetector. The resulting device shows a current rectification ratio of 10 3 , a current photoresponsivity up to 400 A/W in the UV spectral range from 370 to 230 nm, and a low dark current. The detector is practically visible-blind with the UV-to-visible photoresponsivity ratio of 10 5 due to extremely short photocarrier lifetimes in the one-dimensional SWNTs because of strong electron–phonon interactions leading to exciton formation. Finallyl, in this vertical configuration, UV radiation penetrates the top semitransparent SC-SWNT layer with low losses (10–20%) and excites photocarriers within the n-ZnO layer in close proximity to the p-SC-SWNT/n-ZnO interface, where electron–hole pairs are efficiently separated by a high built-in electric field associated with the heterojunction.

36 MATERIALS SCIENCE↗

Electrostatic Gating of Ionic Conductance through Heterogeneous van der Waals Nanopores

Nanofluidic ionic transistors typically require gate voltages above 1 V and operate only at submillimolar ionic strengths, limiting their biocompatible applications. We demonstrate ionic transistors consisting of single sub-10 nm nanopores drilled in van der Waals (vdW) heterostructures with internal gate electrodes made of few-layer graphene. These devices deliver up to 10-fold current modulation at gate voltages as low as 0.3 V in 10 mM KCl, and ∼2-fold modulation at near-physiological 100 mM KCl. Baseline conductance with no gate shows surface-charge-dominated transport below 100 mM KCl, consistent with negatively charged hBN walls and ∼5 nm opening of the pores. The surface charge and the electrochemical asymmetry introduced by the three-electrode configuration govern the device’s behavior: negative gate voltage (V G ) enriches ionic concentrations and enhances current, whereas positive V G induces a local depletion zone that suppresses transport. The current modulation by V G is dependent on the polarity of the transmembrane potential and leads to ion current rectification. Molecular dynamics simulations of a nanopore in a hBN–graphene–hBN stack reveal confinement and surface charge-dependent suppression of the relative permittivity of interfacial water. Continuum modeling with radially varying interfacial water permittivity reproduces the asymmetric I–V characteristics and explains how the embedded gate sculpts local potential and ion concentrations. By enabling sub-0.5 V control of ionic transport at up to 100 mM salt concentrations, these devices address a key need in nanofluidics to create low-power ionic circuits and biosensing.

Materials science↗

Atomically Abrupt Topological p–n Junction

Topological insulators (TI’s) are a new class of quantum matter with extraordinary surface electronic states, which bear great potential for spintronics and error-tolerant quantum computing. In order to put a TI into any practical use, these materials need to be fabricated into devices whose basic units are often p–n junctions. Interesting electronic properties of a ‘topological’ p–n junction were proposed theoretically such as the junction electronic state and the spin rectification. However, the fabrication of a lateral topological p–n junction has been challenging because of materials, process, and fundamental reasons. Here, we demonstrate an innovative approach to realize a p–n junction of topological surface states (TSS’s) of a three-dimensional (3D) topological insulator (TI) with an atomically abrupt interface. When a ultrathin Sb film is grown on a 3D TI of Bi 2 Se 3 with a typical n-type TSS, the surface develops a strongly p-type TSS through the substantial hybridization between the 2D Sb film and the Bi 2 Se 3 surface. Thus, the Bi 2 Se 3 surface covered partially with Sb films bifurcates into areas of n- and p-type TSS’s as separated by atomic step edges with a lateral electronic junction of as short as 2 nm. This approach opens a different avenue toward various electronic and spintronic devices based on well-defined topological p–n junctions with the scalability down to atomic dimensions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Asymmetric Nafion-Coated Nanopore Electrode Arrays as Redox-Cycling-Based Electrochemical Diodes

Inspired by the functioning of cellular ion channels, pore-based structures with nanoscale openings, have been fabricated and integrated into ionic circuits, e.g. ionic diodes and transistors, for signal processing and detection. In these systems, the nonlinear current responses arise either because asymmetric nanopore geometries break the symmetry of the ion distribution, creating unequal surface charge across the nanopore, or by coupling unidirectional electron transfer within a nanopore electrode. Here, we develop a high-performance redox cycling-based electrochemical diode by coating an asymmetric ion-exchange membrane, i.e. Nafion, on the top surface of a nanopore electrode array (Nafion@NEA), in which each pore in the array exhibits one or more annular electrodes. Nafion@NEAs exhibit highly sensitive and charge-selective electroanalytical measurements due to efficient redox cycling reaction, the permselectivity of Nafion, and strong confinement of redox species in the nanopore array. In addition, the top electrode of dual electrode Nafion@NEAs can serve as a voltage-controlled switch to gate ion transport within the nanopore. Thus, Nafion@NEAs can be operated as a diode by switching voltages applied to the top and bottom electrodes of the NEA, leading to a large rectification ratio, fast response times, and simplified circuitry without the need for external electrodes. Here by taking advantage of closely spaced and individually addressable electrodes, the redox cycling electrochemical diode has the potential for application to large-scale production and electrochemically-controlled circuit operations which go well beyond conventional electronic diodes or transistors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anodized Aluminum Oxide Membrane Ionic Memristors

Memory effect in ion transport (IT) at the solid–solution interface is uniquely attractive in that the conductance depends on or “memorizes” the previous states. Hysteretic and rectified transport properties offer exciting potential to developing advanced iontronics and neuromorphic functions, improving the efficiency of energy conversion and electrochemical processes, and overcoming the selectivity-throughput bottleneck in the enrichment of low abundant species for environment- and energy-friendly separations, among others. Herein, memory effects are discovered in the rectified electrokinetic IT through anodized aluminum oxide (AAO) membranes containing densely packed highly ordered nanochannels (10 10 per cm 2 ). Characteristic memristor responses of pinched current–potential loops are resolved in voltammetric experiments and successfully reproduced through finite element simulation. Excitatory and inhibitory conductance states are shown to arise from the enrichment and depletion of mobile charge carriers. Structurewise, the transport symmetry is broken by the barrier oxide layer (BOL) on the one end of the cylindrical nanochannels across the AAO membranes. Charge selectivity is attributed to the gradient(s) of the space charge density across the BOL characterized by depth profiling via X-ray photoelectron spectroscopy analysis. The space charge gradient(s) overcomes the fundamental limitation of widely exploited surface charge effects to enable intense rectification and hysteresis prevailing at very high ionic concentrations up to 1–2 M. A new strategy is developed for controlling the preferential IT direction and selectivity via counterion intercalation and extraction/exchange. Mechanistic understanding is further confirmed through parameter variations such as potential scan rate and ionic strength, which also demonstrates convenient controls of the related functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗