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At least 1,675 records · Page 93

Dielectric Properties of Oligonucleotides on the Surface of Si Nanosandwich Structures

Planar silicon nanostructures that are formed as a very narrow silicon quantum well confined by delta-barriers heavily doped with boron are used to study the dielectric properties of DNA oligonucleotides deposited onto the surface of the nanostructures. The capacitance characteristics of the silicon nanostructures with oligonucleotides deposited onto their surface are determined by recording the local tunneling current- voltage characteristics by means of scanning tunneling microscopy. The results show the possibility of identifying the local dielectric properties of DNA oligonucleotide segments consisting of repeating G–C pairs. These properties apparently give grounds to correlate the segments with polymer molecules exhibiting the properties of multiferroics.

36 MATERIALS SCIENCE↗

Effect of Deep Centers on Charge-Carrier Confinement in InGaN/GaN Quantum Wells and on LED Efficiency

The deep-center-assisted tunneling of carriers in p–n structures of light-emitting diodes (LEDs) with InGaN/GaN quantum wells (QWs) makes smaller the effective height of the injection barrier, but leads to a dependence of the radiation efficiency on the density and energy spectrum of defects in GaN. In the case of hopping conduction across the space charge region, the forward voltage mainly drops near the QW boundary, where the density of deep states at the quasi Fermi-level is the lowest. As a result, band bending at the boundary decreases, and, with increasing current, the direction of the electric field also changes, which leads to a weaker confinement of holes, to their non-radiative recombination in the n barrier, and to an efficiency droop. The low efficiency of green GaN LEDs is associated with the dominance of deep centers and insufficient density of shallow centers in the energy spectrum of defects in barrier layers near the boundaries with the QW. The proposed model is confirmed by the stepwise experimental dependences of the current, capacitance and efficiency of green and blue LEDs in the case of forward bias, which reflect the contribution of color centers responsible for the defect photoluminescence bands in GaN.

36 MATERIALS SCIENCE↗

Electrical Properties and Energy Parameters of n-FeS{sub 2}/p-Cd{sub 1–x}Zn{sub x}Te Heterojunctions

The conditions for fabricating n-FeS{sub 2}/p-Cd{sub 1–x}Zn{sub x}Te heterojunctions by the spray pyrolysis of thin pyrite films on p-Cd{sub 1–x}Zn{sub x}Te crystalline substrates are investigated. A comprehensive analysis of the current–voltage (I–V) and capacitance–voltage (C–V) characteristics makes it possible to establish the limitation of the reverse current by the space-charge region at small reverse biases and consider the mechanisms of current formation with the participation of energy levels near the heterojunction. A model of the energy profile of the n-FeS{sub 2}/p-Cd{sub 1–x}Zn{sub x}Te heterojunction is proposed, which turns out to be in good correspondence with the experimentally determined parameters and the dynamics of their change with a variation in temperature.

36 MATERIALS SCIENCE↗

Effect of Low-Dose Proton Irradiation on the Electrical Characteristics of 4H-SiC Junction Diodes

The effect of low-dose proton irradiation (irradiation dose 10{sup 10}–1.8 × 10{sup 11} cm{sup –2}) on the capacitance–voltage, forward current–voltage, and reverse-recovery characteristics of 4H-SiC p–n{sub o} junction diodes is studied. Irradiation is performed with 1.8-MeV protons through a 10-μm-thick Ni-film (the proton energy and Ni-film thickness were chosen so that the projected proton range in silicon carbide is approximately equal to the p–n{sub o} junction depth). It is shown that proton irradiation in the above doses (i) does not change the concentration of majority carriers, (ii) leads to a dramatic decrease in the lifetime of nonequilibrium carriers (at a low injection level) (by several tens of times at the highest irradiation dose), and (iii) decreases the reverse-recovery charge at a high injection level (by up to a factor of 3 at the highest irradiation dose).

36 MATERIALS SCIENCE↗

Features of the Characteristics of Field-Resistant Silicon–Ultrathin Oxide–Polysilicon Structures

Results of studying the features of the current–voltage (I–V) and capacitance–voltage characteristics of field-resistant silicon–ultrathin oxide–polysilicon structures are presented. It turns out that the total recharging of localized electron states and minority carriers concentrated near the substrate–insulator interface, which occurs with a variation in the field voltage, is an order of magnitude higher than that of samples susceptible to damage by the field stress effect. The tunneling I–V characteristic is significantly asymmetric; notably, the current flowing from the field electrode into the silicon substrate is several orders of magnitude lower when compared with the current flowing from silicon to polysilicon at identical external voltages dropping across the insulating layer. To explain this asymmetry, it is assumed that a potential barrier in the transition layer from polysilicon to oxide, which separates the semiconductor electrode and substrate, has a height of ~1 eV and therefore always hinders electrical transport; for reverse currents, this barrier stops limiting the conductivity as soon as the tunneling level becomes higher than it.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Preparation of Nanosized Tungsten and Tungsten Oxide Powders

Nanopowder tungsten oxide and metallic tungsten are obtained via pyrolysis of ammonium metatungstate. Two methods are used for the synthesis of tungsten oxide: the use of a fibrous matrix and pyrolysis of aerosol particles. Tungsten oxide particles are formed during the pyrolysis in air. Metallic tungsten nanoparticles are obtained via subsequent thermal reduction of tungsten oxide in hydrogen. The structure and morphology of the samples are studied with X-ray diffraction and scanning electron microscopy. Tungsten nanopowders with average sizes from 7 to 30 nm are obtained depending on synthesis temperature. The electrochemical characteristics of electrodes coated with tungsten nanoparticles are studied with cyclic voltammetry, impedance spectroscopy, and galvanostatic charge–discharge methods. An electrode with W nanoparticles exhibited a specific low-frequency capacitance of about 90 F/g due to thin tungsten oxide film on the surface of tungsten nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Defect Mode in Microwave Waveguide Bragg Structures with Metal Pins

A waveguide Bragg structure containing equidistant cylindrical pins that are galvanically coupled to a wide wall of the waveguide is used to implement frequency response functions characterized by the presence of a band gap. Characteristics of a defect mode of the microwave photonic crystal with a pin element as a defect with an n–i–p–i–n structure with controlled conductivity placed in the capacitive gap are experimentally studied and calculated. Controlled reflectance of a microwave signal with a dynamic range of greater than 50 dB is obtained at the frequency of the defect mode.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mechanisms of Frequency-Dependent Conductivity of Mesoporous Silicon at γ Irradiation with Small Doses

Abstract—The effect of low-dose γ radiation on the mechanisms of low-frequency conductivity of mesoporous silicon has been studied. It has been shown that γ irradiation preserves the hopping character of conductivity at a change of the frequency of phonon lattice vibrations, a decrease in the size of the hop, and a shift of the level of the capture of traps to the Fermi level in the band gap, which makes the structure with mesoporous silicon irradiated by γ radiation promising for the creation of multifunctional resistive and capacitive devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development of planar P-type point contact germanium detectors for low-mass dark matter searches

The detection of low-energy deposition in the range of sub-eV through ionization using germanium (Ge) with a bandgap of ~ 0.7 eV requires internal amplification of the charge signal. This can be achieved through high electric field that accelerates charge carriers, which can then generate more charge carriers. The minimum electric field required to generate internal charge amplification is derived for different temperatures. We report the development of a planar point contact Ge detector in terms of its fabrication and the measurements of its leakage current and capacitance as a function of applied bias voltage. With the determination of the measured depletion voltage, the field distribution is calculated using GeFiCa, which predicts that the required electric field for internal charge amplification can be achieved in proximity to the point contact. The energy response to an Am-241 source is characterized and discussed. We conclude that such a detector with internal charge amplification can be used to search for low-mass dark matter.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Electroresponse of weak polyelectrolyte brushes

Abstract End-tethered polyelectrolytes are widely used to modify substrate properties, particularly for lubrication or wetting. External stimuli, such as pH, salt concentration, or an electric field, can induce profound structural responses in weak polyelectrolyte brushes, which can be utilized to further tune substrate properties. We study the structure and electroresponsiveness of weak polyacid brushes using an inhomogeneous theory that incorporates both electrostatic and chain connectivity correlations at the Debye–Hückel level. Our calculation shows that a weak polyacid brush swells under the application of a negative applied potential, in agreement with recent experimental observation. We rationalize this behavior using a scaling argument that accounts for the effect of the surface charge. We also show that the swelling behavior has a direct influence on the differential capacitance, which can be modulated by the solvent quality, pH, and salt concentration. Graphical Abstract

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Physical insights into biological memory using phospholipid membranes

Electrical signals may propagate along neuronal membranes in the brain, thus enabling communication between nerve cells. In doing so, lipid bilayers, fundamental scaffolds of all cell membranes, deform and restructure in response to such electrical activity. These changes impact the electromechanical properties of the membrane, which then physically store biological memory. This memory can exist either over a short or long period of time. Traditionally, biological memory is defined by the strengthening or weakening of transmissions between individual neurons. In this report we show that electrical stimulation may also alter the properties of the lipid membrane, thus pointing toward a novel mechanism for memory storage. Furthermore, based on the analysis of existing electrophysiological data, we study molecular mechanisms underlying the long-term potentiation in phospholipid membranes. Finally, we examine possible relationships between the memory capacitive properties of lipid membranes, neuronal learning, and memory.

59 BASIC BIOLOGICAL SCIENCES↗

Addressing Spacer Channel Resistances in MCDI Using Porous and Pliable Ionic Conductors

Membrane capacitive deionization (MCDI) is a unique electrochemical separations platform that allows for energy recovery during electrode regeneration. Similar to other electrochemical separation technologies producing deionized water (e.g. electrodialysis), ohmic resistances in the spacer channel significantly hampers the performance and energy efficiency of the process. This work devised a series of ionomer coated nylon mesh nets to address spacer channel resistances in MCDI. Under constant current operation, the ionomer coated nylon meshes displayed a 300 mV lower cell voltage rise during deionization while sustaining the same deionization rate. Furthermore, energy recovery was improved by 1.4x to 5.5x depending on the saline feed concentration. The lower cell voltage rise during deionization combined with the greater energy recovery with ionomer coated meshes resulted in energy normalized adsorbed salt (ENAS) values that were 2x to 3x greater. Addressing the spacer channel resistances in MCDI allowed for 8% to 19% increase in current density without the cell voltage exceeding 1.6 V—the upper bound set for mitigating parasitic reactions. Operating at higher current density leads to smaller MCDI units for a given deionization requirement and has implications for reducing the capital costs of the MCDI unit.

Palakkal, Varada Menon (ORCID:0000000317038323)↗

Interpreting Ionic Conductivity for Polymer Electrolyte Fuel Cell Catalyst Layers with Electrochemical Impedance Spectroscopy and Transmission Line Modeling

A cathode catalyst layer containing optimally distributed ionomer is critical to reduce the platinum loading and increase its utilization in polymer electrolyte fuel cells. Here, electrochemical impedance spectroscopy (EIS) was used to measure effective ionic conductivity of pseudo catalyst layers (PCLs) at a relative humidity (RH) range of 50%-120%. These results are compared to previous work using the hydrogen pump (HP) method. EIS effective ionic conductivity results reported here are higher than those from the HP because in the HP set-up ionic pathways must be effectively connected through the PCL to be counted, whereas in the EIS measurement, ionomer segments that are in contact with the membrane but are not effectively connected all the way through the PCL can be detected. Double layer capacitances and effective ionic conductivities of Pt/C catalyst layers with various supports and ionomer to carbon (I/C) ratios were studied. High surface area carbon support resulted in a lower effective ionic conductivity compared to the graphitized carbon support due to worse ionomer dispersion. Effective ionic conductivities of Pt/C layers were compared to that of PCLs. On average, effective ionic conductivities of Pt/C layers were higher than PCLs because of possible carbon agglomeratio n within the PCLs.

25 ENERGY STORAGE↗

Decoupling Conductivity and Solubility in Electrolytes Using Microemulsions

Redox flow batteries have recently received considerable attention as possible large-scale energy storage devices, but their low energy density has inhibited widespread application. In this work, a novel strategy of decoupling conductivity and solubility of electrolytes using microemulsion is put forward to enhance ionic conduction of non-aqueous electrolytes, increase the selectivity of active species, improve the battery voltage, and eventually achieve the possibility of high energy density. We report a study of the electrochemistry of ferrocene in single phase Tween® 20/1-butanol/H 2 O/toluene microemulsion system at 20 °C. At low and intermediate surfactant to water weight ratios (<0.5/0.5), the voltammogram exhibits reversible electrochemical behavior, while at high surfactant levels the curves show lower levels of reversibility. The latter voltammograms have a form typically associated with high resistance in solution, consistent with a gradual transition in microstructure as surfactant levels increase. This change in structure is supported by correlations with conductivity results based on the literature. The voltammograms show little evidence of anomalies in double layer capacitance or electrode "blocking" by droplets, suggesting that the electron transfer is indeed occurring in a facile manner between the electrode and the ferrocene inside the oil phase.

25 ENERGY STORAGE↗

Tuning the Porous Structure in PMMA-Templated Mesoporous MoO 2 for Pseudocapacitive Li-Ion Electrodes

MoO 2 is an exciting candidate for next-generation energy storage. It can be used for fast-charging applications in nanoscale form, but its kinetic performance is often limited by insulating MoO 3 surface oxide layers. Here, we developed methods to produce polymer-templated porous MoO 2 powders where electrical conductivity was well-maintained throughout the structure, even in the presence of some surface oxidation. Porosity, pore size, and crystallite size were controlled by varying the amount and size of the colloidal templates and through calcination temperature. The electrochemical performance was correlated with nanoscale structure: samples with high porosity, medium pore sizes, and good crystallinity display optimal rate capabilities, with over 100 mAh g −1 delivered in 3 min and 93% capacity retention after 1000 cycles. Kinetic studies were performed on samples with the largest and smallest crystallite sizes to understand the charge storage mechanism. In the sample with the smallest crystallite size, 85% of the total stored charge was capacitive, compared to 60% for the largest crystallite size. Sloping voltage profiles in materials with smaller domain sizes further suggest suppression of intercalation-induced phase transitions. This work thus provides insights into the mechanisms of charge storage in nanoscale MoO 2 and design parameters for the production of fast charging materials.

25 ENERGY STORAGE↗

Impedance Modeling for Mixed Conductors with Simultaneous Insertion & Electrocatalytic Reactions: A Case Study of Transition-Metal Hydroxides in Aqueous Electrolyte

Electrochemical impedance spectroscopy (EIS) is commonly used to investigate the kinetics of mixed ionic–electronic conductor (MIEC) electrodes. Across various applications, MIECs exhibit ionic (e.g., insertion) and/or electronic (e.g., electrocatalytic) charge transfer reactions at the electrode/electrolyte interface. Bulk storage and transport of charge carriers also couple with these interfacial reactions. Here, we build a generalized, physics-based impedance model for MIECs with an ion-blocking current collector and explore how bulk and interfacial resistance, chemical capacitance, and DC polarization affect the impedance response. Using transition metal hydroxides as a case study, we provide guidance on extracting reaction kinetics or bulk resistance from the Nyquist plots in interface- or bulk-controlled conditions, respectively. Generalizing our EIS analysis enables a robust analysis of MIEC kinetics for a diverse set of systems.

36 MATERIALS SCIENCE↗

Electrolyzer Performance Loss from Accelerated Stress Tests and Corresponding Changes to Catalyst Layers and Interfaces

Stress tests are developed for proton exchange membrane electrolyzers that utilize low catalyst loading, elevated potential, and frequent cycling with square- and triangle-waves to accelerate anode catalyst layer degradation during intermittent operation. Kinetics drive performance losses (ohmic/transport secondary) and are accompanied by decreasing exchange current density, decreasing cyclic voltammetric capacitance, and increasing polarization resistance. Decreased kinetics are likely due to a combination of iridium (Ir) migration into electrochemically inaccessible locations in the anode or membrane, Ir particle growth (supported by X-ray scattering), changes in the extent of the Ir oxidation state (supported by X-ray absorption spectroscopy), and anode catalyst layer reordering. Decreasing catalyst/transport layer contact and catalyst/membrane interfacial tearing may add contact resistances and account for increasing ohmic losses. Performance losses for low and moderate catalyst loading, as well as from accelerated and model wind/solar cycling protocols, were likewise dominated by kinetics but vary in severity. Additionally, accelerated cycling (1 cycle per minute) appears to reasonably accelerate relevant loss mechanisms and can be used to project electrolyzer lifetime from anode deterioration. Ongoing accelerated stress test development and studies into performance loss mechanisms will continue to be critical as electrolysis shifts to intermittent power and low-cost applications.

30 DIRECT ENERGY CONVERSION↗

Anolyte Enhances Catalyst Utilization and Ion Transport Inside a CO 2 Electrolyzer Cathode

Electrochemical CO 2 reduction is a promising technology to capture and convert CO 2 to valuable chemicals. High Faradaic efficiencies of CO 2 reduction products are achieved with zero-gap alkaline CO 2 electrolyzers with a supporting electrolyte at the anode (anolyte). Herein, we investigate the effect of anolyte on the electrode properties such as catalyst utilization, ionic accessibility etc. of a CO 2 reduction cathode using electrochemical techniques and cell configurations that avoid the complexities related to co-electrolysis. Using 1M KOH as the anolyte and a Cu gas-diffusion-electrode with low Nafion content as the model CO 2 reduction electrode, we find that electrode capacitance (proxy for electrochemically active surface area) and ionic conductivity inside the cathode increase approximately 4 and 447 times, respectively, in presence of KOH. Liquid anolyte wets the electrode’s pore structure more efficiently than capillary condensation of feed water vapor. The ionomer coverage is very low, and its distribution inside the electrode is highly fragmented. Surface ion conduction mechanisms inside the electrode are orders of magnitude lower than the bulk ion conduction in presence of anolyte. This study shows that when an anolyte (e.g., KOH) is used, catalyst utilization and ionic accessibility inside the electrode increase significantly.

30 DIRECT ENERGY CONVERSION↗