Charged Walls Research Articles

Impact of pH-Regulated Wall Charge on the Modulation of Electroosmotic Flow and Transport of Ionic Species through Slit Nanochannels

Impact of pH-Regulated Wall Charge on the Modulation of Electroosmotic Flow and Transport of Ionic Species through Slit Nanochannels

Erasable Domain Wall Current-Dominated Resistive Switching in BiFeO3 Devices with an Oxide-Metal Interface.

Electric transport in the charged domain wall (CDW) region has emerged as a promising phenomenon for the development of next-generation ferro-resistive memory with ultrahigh data storage density. However, accurately measuring the conductivity of CDWs induced by polarization reversal remains challenging due to the polarization modulation of the Schottky barrier at the thin film-electrode interface, which could partially contribute to the collected "on" current of the device. Here, we propose carefully selecting an electrode that can suppress the effect of interfacial barrier modulation induced by polarization reversal, allowing the collected current mainly from the conductive CDWs. The experiment was conducted on epitaxial BiFeO3(001) thin-film devices with vertical and horizontal geometries. Piezo-response force microscopy scanning showed the local polarization experienced 180° rotation to form CDWs under the vertical electric field. However, devices with SrRuO3 epitaxial top electrodes still exhibit an interfacial barrier-dominated diode behavior, with the "on" current proportional to the electrode area. To identify the CDW current, more interfacial defects were introduced by the deposition of Pt top electrodes, which significantly enhanced charge injection for the compensation of the reversed polarization driven by the electric field, leading to the suppressed polarization modulation of the Schottky barrier height. It was observed that the current flow through Pt electrodes is significantly lower compared to that of SRO electrodes and appears to be primarily influenced by the electrode perimeter instead of the electrode area, indicating CDW-dominated conduction behavior in these devices. Planar nanodevices were further fabricated to support the quantitative investigation of the Pt electrode size-dependent "on" current with a linear fit of the current magnitude versus the CDW cross-sectional area. This work constitutes an essential part of understanding the role of the CDW current in ferro-resistive memory devices.

Light-induced strain and its correlation with the optical absorption at charged domain walls in polycrystalline ferroelectrics

Photostrictive materials have a growing interest because of their great potential as light-driven actuators, among other optomechanical applications. In this context, the optical control of macroscopic strain in ferroelectrics has recently attracted remarkable attention as an effective alternative to the conventional electric control of strain. Here, a clear correlation between optical absorption and light-induced strain in polycrystalline BaTiO3 is shown. Specifically, the grain size and the sample thickness dependence of optical absorption when the material is irradiated with energy photons lower than the band gap evidence that light absorption at charged domain walls is the core of the observed photo-response in ferroelectrics. The photoinduced electronic reconstruction phenomenon is proposed as the primary physical mechanism for light absorption at charged domain walls. Results open a new pathway to designing ferroelectric-based devices with new functionalities like thickness gradient-based photo-controlled nanoactuators.

Confined Electrolytes Show Bulk Dynamics Modulated by Hydrodynamic Couplings with the Walls

We use numerical simulations at the mesoscopic scale, namely, multiparticle collision dynamics (MPCD), to investigate the properties of electrolyte solutions in a charged slit pore. The solution is described within the primitive model of electrolytes, where ions are charged hard spheres embedded in a dielectric medium. Hydrodynamic couplings between ions and with the charged walls are precisely accounted for by the MPCD algorithm. We show that the dynamic properties of ions in this situation strongly differ from the behavior at infinite dilution (ideal case), contrary to what is usually assumed in the usual Poisson-Nernst-Planck description of this kind of systems. As a consequence of confinement, the diffusion coefficients of ions unexpectedly increase with the average ionic density in the systems. This is due to a decrease of the proportion of ions that are slowed down by the wall. Moreover, nonequilibrium simulations are used to estimate the electrical conductivity of these confined electrolytes. We show that the simulation results can be accounted for quantitatively by combining bulk descriptions of the electrical conductivity of electrolytes with a simple description of the hydrodynamics of ions in a slit pore.

Mesoscopic theory for ionic liquids and concentrated electrolytes in a slit with charged walls

Concentrated electrolytes and ionic liquids confined between parallel charged plates are studied within a theory combining density functional and field-theoretic methods, extended in this work to the slit geometry. We obtain charge- and density profiles, as well as the excess grand potential as a function of the slit width L in the self-consistent Gaussian approximation. For large density of ions, the obtained disjoining pressure exhibits oscillatory asymptotic decay for increasing L, with the decay length that agrees with the results of recent experiments. On a general level, we show that if the charge density decays with a distance from a charged surface in the oscillatory way, then the electrostatic energy of the slit with charged walls also decays with L in an oscillatory way with the same characteristic lengths. The oscillatory decay disagrees with the asymptotic repulsion obtained in the surface force balance experiments. We argue that in the experiment, the lack of the attraction between the confining surfaces for large L may follow from slow ordering of the isotropic fluid absorbed in the expanding slit into layers with alternating charge.

Computational and theoretical model of electro-osmotic flow pumping in a microchannel with squeezing walls

Numerical simulation and theoretical solution for the electro-osmotic pumping flow of electrolyte solution in a microchannel with squeezing and charged walls are developed in this study. The mathematical model is derived based on using a strong coupling between the nonlinear Poisson–Boltzmann equation and the flow lubrication theory. The governing equations are integrated numerically using the finite difference method. Moreover, an analytical solution to the problem is also obtained using the lubrication theory and is used to solve the Poisson–Boltzmann equation without any approximation technique. The effects of various parameters such as the wall zeta potential, Debye length, and electric field on the fluid pressure distribution, velocity field, and the net flow rate are investigated in detail. The results show that the induced pumping rate depends strongly on the combined effects of the Helmholtz–Smoluchowski, zeta potential, and electrical double layer. Moreover, the produced net flow directionality can be controlled efficiently by manipulating the Helmholtz–Smoluchowski and/or the wall zeta potential. The results obtained from the numerical simulation are then compared with the theoretical analysis and have shown to be in agreement with the proposed mathematical model.

The nanofluidic capacitor: Differential capacitance in the absence of reservoirs.

Within the framework of the classical, mean-field Poisson-Boltzmann (PB) theory, we carry out direct numerical simulations to determine the differential capacitance of a closed nanochannel of a circular cross section, embedded in a polymeric host with charged walls and sealed at both ends by metal electrodes under an external potential bias. Our approach employs the modified PB equation, which accounts for the finite size of ions and the dependency of the electrolyte's relative permittivity on the local electric field. In view of the absence of reservoirs, the modified PB equation becomes subject to global algebraic constraints, without prior knowledge of a bulk electrolyte concentration. Equilibrium ion distributions and differential capacitance curves are investigated as functions of electrolyte properties and the surface charge density modulation. This modulation leads to asymmetric differential capacitance curves that can be tuned. More generally, our approach provides a transparent numerical framework for accurately simulating confined nanofluidic systems with new physical properties that may be exploited in novel iontronic circuit elements.

Charged Domain Walls in BaTiO3 Crystals Emerging from Superdomain Boundaries

AbstractPrevious experiments with barium titanate crystals have shown that electric field applied in the vicinity of its ferroelectric phase transition can be used to introduce peculiar ferroelectric domain walls, persisting to the ambient conditions: head‐to‐head charged walls compensated by the 2D electron gas. The present in situ optical observations allow the documentation of the early stage of this poling process in which the cubic and ferroelectric phases coexist, the latter being broken into multiple martensitic superdomains, separated by superdomain boundaries. It is revealed that the transient superdomains are subsequently converted into the regular ferroelectric domains, while the superdomain boundaries transform into the desired charged domain walls. In order to assign the observed transient domain patterns, to understand the shapes of the observed ferrolectric precipitates and their agglomerates as well as to provide the overall interpretation of the recorded domain formation process, the implications of the mechanical compatibility of the coexisting superdomain states are derived in the framework of the Wechsler–Lieberman–Read theory. These results also suggest that both the electric conductivity and interlinked motion of the superdomain boundaries and phase fronts are involved in the transport of the compensating charge carriers toward the charged domain wall location.

Phenotyping of Methicillin-Resistant Staphylococcus aureus Using a Ratiometric Sensor Array.

Chemical tools capable of classifying multidrug-resistant bacteria (superbugs) can facilitate early-stage disease diagnosis and help guide precision therapy. Here, we report a sensor array that permits the facile phenotyping of methicillin-resistant Staphylococcus aureus (MRSA), a clinically common superbug. The array consists of a panel of eight separate ratiometric fluorescent probes that provide characteristic vibration-induced emission (VIE) profiles. These probes bear a pair of quaternary ammonium salts in different substitution positions around a known VIEgen core. The differences in the substituents result in varying interactions with the negatively charged cell walls of bacteria. This, in turn, dictates the molecular conformation of the probes and affects their blue-to-red fluorescence intensity ratios (ratiometric changes). Within the sensor array, the differences in the ratiometric changes for the probes result in "fingerprints" for MRSA of different genotypes. This allows them to be identified using principal component analysis (PCA) without the need for cell lysis and nucleic acid isolation. The results obtained with the present sensor array agree well with those obtained using polymerase chain reaction (PCR) analysis.

Characterization of the Nonlinear Electrophoretic Behavior of Colloidal Particles in a Microfluidic Channel

Contemporary findings in the field of insulator-based electrokinetics have demonstrated that in systems under the influence of direct current (DC) fields, dielectrophoresis (DEP) is not the main electrokinetic mechanism responsible for particle manipulation but rather the sum of electroosmosis, linear and nonlinear electrophoresis. Recent microfluidic studies have brought forth a methodology capable of experimentally estimating the nonlinear electrophoretic mobility of colloidal particles. This methodology, however, is limited to particles that fit two conditions: (i) the particle charge has the same sign as the channel wall charge and (ii) the magnitude of the particle ζ-potential is lower than that of the channel wall. The present work aims to expand upon this methodology by including particles whose ζ-potential has a magnitude larger than that of the wall, referred to as "type 2" particles, as well as to report findings on particles that appear to still be under the influence of the linear electrophoretic regime even at extremely high electric fields (∼6000 V/cm), referred to as "type 3" particles. Our findings suggest that both particle size and charge are key parameters in the determination of nonlinear electrophoretic properties. Type 2 microparticles were all found to be small (diameter ∼ 1 μm) and highly charged, with ζ-potentials above -60 mV; in contrast, type 3 microparticles were all large with ζ-potentials between -40 and -50 mV. However, it was also hypothesized that other nonconsidered parameters could be influencing the results, especially at higher electric fields (>3000 V/cm). The present work also aims to identify the current limitations in the experimental determination of μEP,NL and propose a framework for future work to address the current gaps in the evolving topic of nonlinear electrophoresis of colloidal particles.

Charge carrier transport and polarization in M/PZT/M structures

A model of non-stationary charge carrier transport in M/PZT/M ferroelectric structures has been developed. It is assumed that, at room temperature, electrons generated by oxygen vacancies are captured by Ti+3 levels and move between them under the action of electric fields caused by the external bias and polarization. The polarization distribution in a PZT film is described with varying degrees of complexity, from a constant value outside the defect layers to one determined by the equation following from the Landau–Ginzburg theory. The numerical simulation performed made it possible to explain the reasons and conditions for the appearance of current–voltage characteristics with unusual current peaks, to show the existence of several solutions in the Landau–Ginzburg model for a film with Schottky barriers, and to reveal the response of charged domain walls to an applied voltage.

Antimicrobial Peptides: A Promising Strategy for Anti-tuberculosis Therapeutics.

The high global burden of tuberculosis (TB) and the increasing emergence of the drugresistant (DR) strain of Mycobacterium tuberculosis (Mtb) emphasize the urgent need for novel antimycobacterial agents. Antimicrobial peptides (AMPs) are small peptides widely existing in a variety of organisms and usually have amphiphilic cationic structures, which have a selective affinity to the negatively charged bacterial cell wall. Besides direct bactericidal mechanisms, including interacting with the bacterial cell membrane and interfering with the biosynthesis of the cell wall, DNA, or protein, some AMPs are involved in the host's innate immunity. AMPs are promising alternative or complementary agents for the treatment of DR-TB, given their various antibacterial mechanisms and low cytotoxicity. A large number of AMPs, synthetic or natural, from human to bacteriophage sources, have displayed potent anti-mycobacterial activity in vitro and in vivo. In this review, we summarized the features, antimycobacterial activity, and mechanisms of action of the AMPs according to their sources. Although AMPs have not yet met the expectations for clinical application due to their low bioavailabilities, high cost, and difficulties in large-scale production, their potent antimycobacterial activity and action mechanisms, which are different from conventional antibiotics, make them promising antibacterial agents against DR-Mtb in the future.

Visible-Light-Control of Dielectric Permittivity in Ferroelectrics with Charged Domain Walls

Optical control of functional properties in ferroic materials is now a highly appealing topic because it may entail different paradigms for future technologies. In ferroelectrics, in particular, controlling the properties with light implies noncontact external control of the material's functionality, thereby opening a pathway for developing the next generation of photocontrolled devices. Recently, experimental observations have demonstrated that the dielectric permittivity of charged-domain-wall ferroelectrics can be easily modulated by visible light. However, because of the wide band gap of ferroelectric materials, the physical origin of this phenomenon is still controversial. Here, the photoinduced electronic reconstruction mechanism is proposed as the primary light-absorption mechanism in charged domain walls, allowing an understanding of the origin of the visible-light control of dielectric permittivity in ferroelectric materials.

Boron nitride nanotube–salt–water hybrid:crystalline precipitation

Molecular dynamics simulation is used to study the transport characteristics of NaCl solution in boron nitride nanotubes (BNNTs). It presents an interesting and well-supported MD study of the crystallization of NaCl from its water solution under the confinement of a 3 nm thick boron nitride nanotube with varied surface charging conditions. The results of the molecular dynamics simulation indicate that NaCl crystallization occurs in charged BNNTs at room temperature when the concentration of NaCl solution reaches about 1.2 M. The reason for this phenomenon is as follows: when the number of ions in the nanotubes is high, the double electric layer that forms at the nanoscale near the charged wall surface, the hydrophobicity of BNNTs, and the interaction among ions cause ions to aggregate in the nanotubes. As the concentration of NaCl solution increases, the concentration of ions when they aggregate in the nanotubes reaches the saturation concentration of the NaCl solution, resulting in the crystalline precipitation phenomenon.

Calcium-binding motif-mediated binding of redundant calcium offers a chimeolysin enhanced bactericidal activity and extended host range under physiological conditions.

Calcium-binding motifs are shared by multiple bacteriophage lysins; however, the influence of calcium on the enzymatic activity and host range of these enzymes is still not understood. To address this, ClyF, a chimeric lysin with a putative calcium-binding motif, was used as a model for in vitro and in vivo investigations. The concentration of calcium bound to ClyF was determined by atomic absorption spectrometry. The influence of calcium on the structure, activity and host range of ClyF was assessed by circular dichroism and time-kill assays. The bactericidal activity of ClyF was evaluated in various sera and a mouse model of Streptococcus agalactiae bacteraemia. ClyF has a highly negatively charged surface around the calcium-binding motif that can bind extra calcium, thereby increasing the avidity of ClyF for the negatively charged bacterial cell wall. In line with this, ClyF exhibited significantly enhanced staphylolytic and streptolytic activity in various sera containing physiological calcium, including human serum, heat-inactivated human serum, mouse serum and rabbit serum. In a mouse model of S. agalactiae bacteraemia, intraperitoneal administration of a single dose of 25 μg/mouse ClyF fully protected the mice from lethal infection. The present data collectively showed that physiological calcium improves the bactericidal activity and host range of ClyF, making it a promising candidate for the treatment of infections caused by multiple staphylococci and streptococci.

Three-dimensional pattern in dielectric barrier discharge with modulated gas gap

We report a three-dimensional pattern with self-organization in three spatial dimensions in dielectric barrier discharge (DBD) by designing a novel device with modulated gas gap. The distribution of electric field by solving the Poisson equation in the x-y plane varies along the z-axis, and three kinds of gas gaps with different thicknesses have different electric fields. The spatiotemporal dynamics of the pattern is obtained by photomultiplier tubes and intensified charge-coupled device. For estimating the plasma parameters, the emission optical spectra are detected by a spectrograph. In three gas gaps, there are five substructures with different morphologies and plasma states in which two structures discharge at the falling edge of the applied voltage. The variation along the z-axis demonstrates that a three-dimensional pattern is truly obtained. It exhibits some novel phenomena that should advance plasma physics in DBD and pattern dynamics as follows. At the falling edge discharge, the discharge moment of a substructure is dependent upon the polarity of the electrode where the gas gap is close. The variation trend of the molecular vibration temperatures is opposite to that of the electron density whether at the rising or the falling edge of the applied voltage for five substructures. The difference between spatial distribution of the substructure and that of the corresponding electric field indicates the effects of the wall charges. Overall, the formation of the pattern includes the resonance of multiple waves by exciting two pre-set wave vectors at different positions of the z-axis and the self-organization effect caused by the wall charge.

Charged domain walls in lithium niobate and lithium tantalate crystals with composition gradients

The formation of charged domain walls (CDWs) in the bulk was studied in lithium tantalate LiTaO3 (LT) and lithium niobate LiNbO3 (LT) crystals with various composition gradients along the polar axis produced by partial vapor transport equilibration (VTE). Under the action of the pyroelectric field upon cooling after the phase transition, the shape of a CDW in LT changed significantly, in contrast to LN: the ledges appeared at CDW and grew toward the polar surfaces. The creation of tail-to-tail and head-to-head CDWs with controlled shape is important for various applications.

Domain structure evolution during polarization reversal in calcium orthovanadate single crystals

The domain structure evolution under the action of the series of rectangular electric field pulses at the elevated temperature has been studied by in situ optical imaging in calcium orthovanadate single crystal with an as-grown domain structure. In contrast to the usual continuous domain wall motion, the arising of domains with immovable walls at the surface as a result of ledge growth from the charged domain wall (CDW) was obtained. The imaging of the static domain structure at the polar surface allowed for determining the correlation between positions of the domains and CDWs. The switching after termination of the external field was observed.

Polarization reversal in the uniaxial ferroelectric under full compensation of depolarization field

The role of charge conservation law in our understanding of the peculiarities of the polarization reversal process in ferroelectrics is discussed. The example of the uniaxial ferroelectric LiNbO3 with bi-domain tail-to-tail structure is compared with traditional switching from the single domain state. The crucial role of the enhanced conductivity along charged domain walls arising due to switching in such structures is discussed.

Electromechanics of Domain Walls in Uniaxial Ferroelectrics

AbstractPiezoresponse force microscopy (PFM) is used for investigation of the electromechanical behavior of the head‐to‐head (H‐H) and tail‐to‐tail (T‐T) domain walls on the non‐polar surfaces of three uniaxial ferroelectric materials with different crystal structures: LiNbO3, Pb5Ge3O11, and ErMnO3. It is shown that, contrary to the common expectation that the domain walls should not exhibit any PFM response on the non‐polar surface, an out‐of‐plane deformation of the crystal at the H‐H and T‐T domain walls occurs even in the absence of the out‐of‐plane polarization component due to a specific form of the piezoelectric tensor. In spite of their different symmetry, in all studied materials, the dominant contribution comes from the counteracting shear strains on both sides of the H‐H and T‐T domain walls. The finite element analysis approach that takes into account a contribution of all elements in the piezoelectric tensor, is applicable to any ferroelectric material and can be instrumental for getting a new insight into the coupling between the electromechanical and electronic properties of the charged ferroelectric domain walls.