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At least 703 records · Page 39

Ion acoustic solitons and supersolitons in a magnetized plasma with nonthermal hot electrons and Boltzmann cool electrons

Arbitrary amplitude, ion acoustic solitons, and supersolitons are studied in a magnetized plasma with two distinct groups of electrons at different temperatures. The plasma consists of a cold ion fluid, cool Boltzmann electrons, and nonthermal energetic hot electrons. Using the Sagdeev pseudo-potential technique, the effect of nonthermal hot electrons on soliton structures with other plasma parameters is studied. Our numerical computation shows that negative potential ion-acoustic solitons and double layers can exist both in the subsonic and supersonic Mach number regimes, unlike the case of an unmagnetized plasma where they can only exist in the supersonic Mach number regime. For the first time, it is reported here that in addition to solitions and double layers, the ion-acoustic supersoliton solutions are also obtained for certain range of parameters in a magnetized three-component plasma model. The results show good agreement with Viking satellite observations of the solitary structures with density depletions in the auroral region of the Earth's magnetosphere.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Origin of the 2D Electron Gas at the SrTiO 3 Surface

Bulk SrTiO 3 is a well-known band insulator and the most common substrate used in the field of complex oxide heterostructures. Its surface and interface with other oxides, however, have demonstrated a variety of remarkable behaviors distinct from those expected. In this work, using a suite of in situ techniques to monitor both the atomic and electronic structures of the SrTiO 3 (001) surface prior to and during growth, the disappearance and re-appearance of a 2D electron gas (2DEG) is observed after the completion of each SrO and TiO 2 monolayer, respectively. The 2DEG is identified with the TiO 2 double layer present at the initial SrTiO 3 surface, which gives rise to a surface potential and mobile electrons due to vacancies within the TiO 2-x adlayer. Much like the electronic reconstruction discovered in other systems, two atomic planes are required, here supplied by the double layer. The combined in situ scattering/spectroscopy findings resolve a number of longstanding issues associated with complex oxide interfaces, facilitating the employment of atomic-scale defect engineering in oxide electronics.

2D electron gas↗

Sharp transition between two regimes of operation of dc discharge with two anodes and thermionic emission from cathode

In a dc discharge plasma with two anodes and thermionic emission from cathode, the two anodes are used for plasma control. The main anode is placed between the cathode and the other auxiliary anode has a circular opening for passing electron current from the cathode to the second anode. It is experimentally demonstrated that a plasma may exhibit a sudden transition between two quasi-stable conditions as one increases the cathode-electron current collected by the auxiliary anode through an aperture, i.e., hole, in the main anode. In one regime, a bright glowing “ball-shaped double layer” appears on the plasma side having a potential drop of 10–15 eV and concomitant ionization in the neighboring region attached to the opening. The second regime is characterized by a uniform potential profile in plasma and an absence of the ball-shaped double layer. The transition between these regimes is accompanied by a significant change in plasma properties, such as the electron energy distribution function (EEDF). Controlling the EEDF is a valuable capability in technological applications. Increasing the gas pressure leads to the elimination of the first regime for sufficiently high gas pressure, the threshold being a few Torr. The disappearance of a regime transition can be explained by invoking an EEDF transition, from being nonlocal at low pressure to becoming local at high pressure. Local EEDF is determined by local values of electric field. Nonlocal EEDF is determined by electric field values elsewhere, and the electron can travel without energy loss over a path much longer than the discharge dimension.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Electrostatic and electrochemical tuning of superconductivity in two-dimensional NbSe{sub 2} crystals

We report modulation of the superconducting critical temperature (T{sub c}) of ultrathin niobium diselenide (NbSe{sub 2}) single crystals by gating an electric double-layer transistor. We realized reversible and irreversible changes of the T{sub c} by adjusting the operating range of the voltage. The reversible and irreversible responses correspond to the electrostatic carrier doping and the electrochemical etching of the crystal, respectively. The results suggest that electric double-layer gating provides opportunities to control and functionalize collective electronic phenomena in two-dimensional crystals.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electronic and optical properties of novel carbon allotropes

The vibrational properties, electronic structures and optical properties of novel carbon allotropes, such as monolayer penta-graphene (PG), double-layer PG and T12-carbon, were studied by first-principles calculations. Results of phonon calculations demonstrate that these exotic carbon allotropes are dynamically stable. The bulk T12 phase is an indirect-gap semiconductor having a quasiparticle (QP) bandgap of ~5.19 eV. When the bulk material transforms to a two-dimensional (2D) phase, the monolayer and double-layer PG become quasi-direct gap semiconductors with smaller QP bandgaps of ~4.48 eV and ~3.67 eV, respectively. Furthermore, the partial charge density analysis indicates that the 2D phases retain part of the electronic characteristics of the T12 phase. The linear photon energy-dependent dielectric functions and related optical properties including refractive index, extinction coefficient, absorption spectrum, reflectivity, and energy-loss spectrum were also computed and discussed. Additionally, the chemical stability of monolayer PG and the electronic and optical properties of double-side hydrogenated monolayer PG were also investigated. Furthermore, the results obtained from our calculations are beneficial to practical applications of these exotic carbon allotropes in optoelectronics and electronics.

36 MATERIALS SCIENCE↗

Traditional Semiconductors in the Two-Dimensional Limit

Interest in two-dimensional materials has exploded in recent years. Not only are they studied due to their novel electronic properties, such as the emergent Dirac fermion in graphene, but also as a new paradigm in which stacking layers of distinct two-dimensional materials may enable different functionality or devices. Here, through first-principles theory, we reveal a large new class of two-dimensional materials which are derived from traditional III-V, II-VI, and I-VII semiconductors. It is found that in the ultrathin limit the great majority of traditional binary semiconductors studied (a series of 28 semiconductors) are not only kinetically stable in a two-dimensional double layer honeycomb structure, but more energetically stable than the truncated wurtzite or zinc-blende structures associated with three dimensional bulk. These findings both greatly increase the landscape of two-dimensional materials and also demonstrate that in the double layer honeycomb form, even ordinary semiconductors, such as GaAs, can exhibit exotic topological properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Understanding cation effects in electrochemical CO 2 reduction

Solid–liquid interface engineering has recently emerged as a promising technique to optimize the activity and product selectivity of the electrochemical reduction of CO 2 . In particular, the cation identity and the interfacial electric field have been shown to have a particularly significant impact on the activity of desired products. Using a combination of theoretical and experimental investigations, we show the cation size and its resultant impact on the interfacial electric field to be the critical factor behind the ion specificity of electrochemical CO 2 reduction. We present a multi-scale modeling approach that combines size-modified Poisson–Boltzmann theory with ab initio simulations of field effects on critical reaction intermediates. The model shows an unprecedented quantitative agreement with experimental trends in cation effects on CO production on Ag, C 2 production on Cu, CO vibrational signatures on Pt and Cu as well as Au(111) single crystal experimental double layer capacitances. The insights obtained represent quantitative evidence for the impact of cations on the interfacial electric field. Lastly, we present design principles to increase the activity and selectivity of any field-sensitive electrochemical process based on the surface charging properties: the potential of zero charge, the ion size, and the double layer capacitance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilized shear thickening electrolyte

A passively impact resistant composite electrolyte composition includes an aprotic electrolyte solvent, from 0.5 to 6M of an electrolyte salt, and shear thickening particles having a polydispersity index of no greater than 0.1, an average particle size in a range of 50 nm to 1 um, and an absolute zeta potential of greater than ±40 mV. The shear thickening particles have thereon an electrochemical double layer. The composition further includes a stabilizing surfactant. The stabilizing surfactant includes a first portion for adsorbing to the particles, and a second portion that is absorbed in the solvent. The length of the surfactant from the first portion to the second portion is greater than twice the thickness of the electrochemical double layer. Batteries and electrochemical devices incorporating the electrolyte composition are disclosed. Methods of making the electrolyte composition and of operating a battery are also disclosed.

Veith, Gabriel M.↗

Four-Terminal Electrochemistry: A Back-Gate Controls the Electrochemical Potential of a 2D Working Electrode

We demonstrate that ultrathin semiconductor working electrodes integrated into metal–insulator–semiconductor (MIS) stacks are an enabling platform for understanding non-Faradaic semiconductor electrochemistry. Furthermore, 5 nm thick ZnO electrodes were deposited on 30 nm HfO 2 dielectric on a Pd “gate” electrode. Application of a bias V G between the Pd gate and the ZnO electrode causes electrons to accumulate in the ZnO layer as measured by recording the in-plane sheet conductance. By contacting the top surface of the ZnO layer with the electrolyte in a conventional three-electrode electrochemical cell, we show that the gate voltage V G modulates the electrochemical potential V ZnO of the ZnO film with respect to a reference electrode. Electrochemical potential changes ΔV ZnO up to –1 V vs Ag/Ag + are achieved for V G = +7 V. Furthermore, by measuring V ZnO vs V G , we extract the quantum capacitance CQ of the ZnO film as a function of the Fermi-level position, which provides a direct measure of the ZnO electronic density of states (DOS). Finally, we demonstrate that the gated ZnO working electrodes can disentangle the two principal components of electrochemical potential, namely, the Fermi-level shift Δδ and the double-layer charging energy eΔΦ EDL . This disentanglement hinges on a fundamental difference between back-gating and normal electrochemical control, namely, that electrochemical control requires double-layer charging, while back-gate control does not. Collectively, the results show that the backside gate electrode is an effective fourth terminal that enables measurements that are difficult to achieve in conventional three-terminal electrochemical setups.

36 MATERIALS SCIENCE↗

Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods

A nano-structured drug-inorganic clay hybrid involving an active anticancer compound, which is chlorogenic acid (CA) intercalated into Zn/Al-layered double hydroxide, has been assembled via ion-exchange and co-precipitation methods to form a nanohybrid CZAE (a chlorogenic acid-Zn/Al nanohybrid synthesised using an ion-exchange method) and CZAC (a chlorogenic acid-Zn/Al nanohybrid synthesised using a direct method), respectively. The X-ray diffraction (XRD) results confirmed that the CA-LDH had a hybrid structure in which the anionic chlorogenate is arranged between the interlayers as a horizontal monolayer at 90 and 20° angles from the x axis for CZAE and CZAC, respectively. Both nanohybrids have the properties of mesoporous materials. The high loading percentage of chlorogenic acid (approximately 43.2% for CZAE and 45.3% for CZAC) with basal spacings of 11.7 and 12.6 Å for CZAE and CZAC, respectively, corroborates the successful intercalation of chlorogenic acid into the interlayer gallery of layered double hydroxides. Free chlorogenic acid and the synthesised nanocomposites (CZAE, CZAC) were assessed for their cytotoxicity against various cancer cells. The Fourier transform infrared data supported the formation of both nanohybrids, and a thermal analysis showed that the nanohybrids are more thermally stable than their counterparts. The chlorogenate shows a sustained release, and the release rate of chlorogenate from CZAE and CZAC nanohybrids at pH 7.4 is remarkably lower than that at pH 4.8 due to their different release mechanisms. The release rate of chlorogenate from both nanohybrids can be described as pseudo-second order. The present investigation revealed the potential of the nanohybrids to enhance the in vitro anti-tumour effect of chlorogenic acid in liver and lung cancer cells in vitro. - Highlights: • We intercalated chlorogenic into Zn/Al-layered double hydroxide by ion-exchange and coprecipitation methods. • The two methods gave nanocomposites with slightly different physico-chemical properties. • Chlorogenate-zinc aluminium layered double hydroxide nanohybrids have the potential to be used as a controlled release formulation. • The thermal stability of chlorogenic acid is markedly enhanced upon the intercalation process. • The inhibition of cancer cell growth is higher for nanohybrids than for free chlorogenic acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks

Abstract Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni 3 (HIR 3 ‐TAT) 2 (TAT=triazatruxene; R=H, Et, n ‐Bu, n ‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni 3 (HIH 3 ‐TAT) 2 to Ni 3 (HIBu 3 ‐TAT) 2 . Partial exfoliation of Ni 3 (HIBu 3 ‐TAT) 2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.

Su, Alice Y.↗

Electrochemical Capacitance Traces with Interlayer Spacing in Two‐dimensional Conductive Metal–Organic Frameworks

Abstract Electrically conductive metal–organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double‐layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure‐function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene‐based 2D layered conductive MOFs with variable alkyl functional groups, Ni 3 (HIR 3 ‐TAT) 2 (TAT=triazatruxene; R=H, Et, n ‐Bu, n ‐Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in‐plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double‐layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni 3 (HIH 3 ‐TAT) 2 to Ni 3 (HIBu 3 ‐TAT) 2 . Partial exfoliation of Ni 3 (HIBu 3 ‐TAT) 2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox‐active sites may motivate further design and engineering of electrode materials for EC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical and laboratory simulations of auroral acceleration

The existence of parallel electric fields is an essential ingredient of auroral physics, leading to the acceleration of particles that give rise to the auroral displays. An auroral flux tube is modelled using electrostatic Vlasov simulations, and the results are compared to simulations of a proposed laboratory device that is meant for studies of the plasma physical processes that occur on auroral field lines. The hot magnetospheric plasma is represented by a gas discharge plasma source in the laboratory device, and the cold plasma mimicking the ionospheric plasma is generated by a Q-machine source. In both systems, double layers form with plasma density gradients concentrated on their high potential sides. The systems differ regarding the properties of ion acoustic waves that are heavily damped in the magnetosphere, where the ion population is hot, but weakly damped in the laboratory, where the discharge ions are cold. Ion waves are excited by the ion beam that is created by acceleration in the double layer in both systems. The efficiency of this beam-plasma interaction depends on the acceleration voltage. For voltages where the interaction is less efficient, the laboratory experiment is more space-like.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Organic/inorganic hybrid synaptic transistors gated by proton conducting methylcellulose films

The idea of building a brain-inspired cognitive system has been around for several decades. Recently, electric-double-layer transistors gated by ion conducting electrolytes were reported as the promising candidates for synaptic electronics and neuromorphic system. In this letter, indium-zinc-oxide transistors gated by proton conducting methylcellulose electrolyte films were experimentally demonstrated with synaptic plasticity including paired-pulse facilitation and spatiotemporal-correlated dynamic logic. More importantly, a model based on proton-related electric-double-layer modulation and stretched-exponential decay function was proposed, and the theoretical results are in good agreement with the experimentally measured synaptic behaviors.

36 MATERIALS SCIENCE↗

Voltage-induced modulation of interfacial ionic liquids measured using surface plasmon resonant grating nanostructures

We have used surface plasmon resonant metal gratings to induce and probe the dielectric response (i.e., electro-optic modulation) of ionic liquids (ILs) at electrode interfaces. Here, the cross-plane electric field at the electrode surface modulates the refractive index of the IL due to the Pockels effect. This is observed as a shift in the resonant angle of the grating (i.e., Δϕ), which can be related to the change in the local index of refraction of the electrolyte (i.e., Δnlocal). The reflection modulation of the IL is compared against a polar (D2O) and a non-polar solvent (benzene) to confirm the electro-optic origin of resonance shift. The electrostatic accumulation of ions from the IL induces local index changes to the gratings over the extent of electrical double layer (EDL) thickness. Finite difference time domain simulations are used to relate the observed shifts in the plasmon resonance and change in reflection to the change in the local index of refraction of the electrolyte and the thickness of the EDL. Simultaneously using the wavelength and intensity shift of the resonance enables us to determine both the effective thickness and Δn of the double layer. We believe that this technique can be used more broadly, allowing the dynamics associated with the potential-induced ordering and rearrangement of ionic species in electrode–solution interfaces.

Chemistry↗

Low-Temperature Supercapacitors

An effort to extend the low-temperature operational limit of supercapacitors is currently underway. At present, commercially available non-aqueous supercapacitors are rated for a minimum operating temperature of -40 C. A capability to operate at lower temperatures would be desirable for delivering power to systems that must operate in outer space or in the Polar Regions on Earth. Supercapacitors (also known as double-layer or electrochemical capacitors) offer a high power density (>1,000 W/kg) and moderate energy density (about 5 to 10 Wh/kg) technology for storing energy and delivering power. This combination of properties enables delivery of large currents for pulsed applications, or alternatively, smaller currents for low duty cycle applications. The mechanism of storage of electric charge in a supercapacitor -- at the electrical double-layer formed at a solid-electrode/liquid-electrolyte interface -- differs from that of a primary or secondary electrochemical cell (i.e., a battery) in such a manner as to impart a long cycle life (typically >10(exp 6) charge/discharge cycles).

Brandon, Erik J.↗

Energy storage device including a redox-enhanced electrolyte

An electrical double layer capacitor (EDLC) energy storage device is provided that includes at least two electrodes and a redox-enhanced electrolyte including two redox couples such that there is a different one of the redox couples for each of the electrodes. When charged, the charge is stored in Faradaic reactions with the at least two redox couples in the electrolyte and in a double-layer capacitance of a porous carbon material that comprises at least one of the electrodes, and a self-discharge of the energy storage device is mitigated by at least one of electrostatic attraction, adsorption, physisorption, and chemisorption of a redox couple onto the porous carbon material.

25 ENERGY STORAGE↗

Existence domains of dust-acoustic solitons and supersolitons

Using the Sagdeev potential method, the existence of large amplitude dust-acoustic solitons and supersolitons is investigated in a plasma comprising cold negative dust, adiabatic positive dust, Boltzmann electrons, and non-thermal ions. This model supports the existence of positive potential supersolitons in a certain region in parameter space in addition to regular solitons having negative and positive potentials. The lower Mach number limit for supersolitons coincides with the occurrence of double layers whereas the upper limit is imposed by the constraint that the adiabatic positive dust number density must remain real valued. The upper Mach number limits for negative potential (positive potential) solitons coincide with limiting values of the negative (positive) potential for which the negative (positive) dust number density is real valued. Alternatively, the existence of positive potential solitons can terminate when positive potential double layers occur.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗