Ionic Gating Research Articles

Exploration of exciton behavior in atomically thin WS2 layers by ionic gating

The photoluminescence spectra of mono- and bilayer WS2, gated by the ionic liquid, were systematically studied at 77 K. Interesting phenomena, such as a redshift of the exciton peaks and a change in the spectral weight of the exciton, trion, and biexciton peaks, were observed at intermediate doping levels. By increasing the doping level, all the exciton, trion, and biexciton peaks vanished, which is attributed to the phase-space filling effect and the Coulomb screening effect. The variation in the band structure, which was induced by the quantum-confined Stark effect in both the mono- and bilayer WS2, was also studied using first-principle calculations.

Electric-field control of magnetism in a few-layered van der Waals ferromagnetic semiconductor.

Manipulating a quantum state via electrostatic gating has been of great importance for many model systems in nanoelectronics. Until now, however, controlling the electron spins or, more specifically, the magnetism of a system by electric-field tuning has proven challenging1-4. Recently, atomically thin magnetic semiconductors have attracted significant attention due to their emerging new physical phenomena5-13. However, many issues are yet to be resolved to convincingly demonstrate gate-controllable magnetism in these two-dimensional materials. Here, we show that, via electrostatic gating, a strong field effect can be observed in devices based on few-layered ferromagnetic semiconducting Cr2Ge2Te6. At different gate doping, micro-area Kerr measurements in the studied devices demonstrate bipolar tunable magnetization loops below the Curie temperature, which is tentatively attributed to the moment rebalance in the spin-polarized band structure. Our findings of electric-field-controlled magnetism in van der Waals magnets show possibilities for potential applications in new-generation magnetic memory storage, sensors and spintronics.

Anomalous screening of an electrostatic field at the surface of niobium nitride

The interaction between an electric field and the electric charges in a material is described by electrostatic screening, which in metallic systems is commonly thought to be confined within a distance of the order of the Thomas–Fermi length. The validity of this picture, which holds for surface charges up to ∼1013 cm−2, has been recently questioned by several experimental results when dealing with larger surface charges, such as those routinely achieved via the ionic gating technique. Whether these results can be accounted for in a purely electrostatic picture is still debated. In this work, we tackle this issue by calculating the spatial dependence of the charge carrier density in thin slabs of niobium nitride via an ab initio density functional theory approach in the field-effect transistor configuration. We find that perturbations induced by surface charges ≲1014 cm−2 are mainly screened within the first layer, while those induced by larger surface charges ∼1015 cm−2 can penetrate over multiple atomic layers, in reasonable agreement with the available experimental data. Furthermore, we show that a significant contribution to the screening of large fields is associated not only to the accumulation layer of the induced charge carriers at the surface, but also to the polarization of the pre-existing charge density of the undoped system.

Synergistic Gating of Electro-Iono-Photoactive 2D Chalcogenide Neuristors: Coexistence of Hebbian and Homeostatic Synaptic Metaplasticity.

Emulation of brain-like signal processing with thin-film devices can lay the foundation for building artificially intelligent learning circuitry in future. Encompassing higher functionalities into single artificial neural elements will allow the development of robust neuromorphic circuitry emulating biological adaptation mechanisms with drastically lesser neural elements, mitigating strict process challenges and high circuit density requirements necessary to match the computational complexity of the human brain. Here, 2D transition metal di-chalcogenide (MoS2 ) neuristors are designed to mimic intracellular ion endocytosis-exocytosis dynamics/neurotransmitter-release in chemical synapses using three approaches: (i) electronic-mode: a defect modulation approach where the traps at the semiconductor-dielectric interface are perturbed; (ii) ionotronic-mode: where electronic responses are modulated via ionic gating; and (iii) photoactive-mode: harnessing persistent photoconductivity or trap-assisted slow recombination mechanisms. Exploiting a novel multigated architecture incorporating electrical and optical biases, this incarnation not only addresses different charge-trapping probabilities to finely modulate the synaptic weights, but also amalgamates neuromodulation schemes to achieve "plasticity of plasticity-metaplasticity" via dynamic control of Hebbian spike-time dependent plasticity and homeostatic regulation. Coexistence of such multiple forms of synaptic plasticity increases the efficacy of memory storage and processing capacity of artificial neuristors, enabling design of highly efficient novel neural architectures.

Ion Gated Synaptic Transistors Based on 2D van der Waals Crystals with Tunable Diffusive Dynamics.

Neuromorphic computing represents an innovative technology that can perform intelligent and energy-efficient computation, whereas construction of neuromorphic systems requires biorealistic synaptic elements with rich dynamics that can be tuned based on a robust mechanism. Here, an ionic-gating-modulated synaptic transistor based on layered crystals of transitional metal dichalcogenides and phosphorus trichalcogenides is demonstrated, which produce a diversity of short-term and long-term plasticity including excitatory postsynaptic current, paired pulse facilitation, spiking-rate-dependent plasticity, dynamic filtering, etc., with remarkable linearity and ultralow energy consumption of ≈30 fJ per spike. Detailed transmission electron microscopy characterization and ab initio calculation reveal two-stage ionic gating effects, namely, surface adsorption and internal intercalation in the channel medium, causing different poststimulation diffusive dynamics and thus accounting for the observed short-term and long-term plasticity, respectively. The synaptic activity can therefore be effectively manipulated by tailoring the ionic gating and consequent diffusion dynamics with varied thickness and structure of the van der Waals material as well as the number, duration, rate, and polarity of gate stimulations, making the present synaptic transistors intriguing candidates for low-power neuromorphic systems.

Inducing ferromagnetism and Kondo effect in platinum by paramagnetic ionic gating.

Electrically controllable magnetism, which requires the field-effect manipulation of both charge and spin degrees of freedom, has attracted growing interest since the emergence of spintronics. We report the reversible electrical switching of ferromagnetic (FM) states in platinum (Pt) thin films by introducing paramagnetic ionic liquid (PIL) as the gating media. The paramagnetic ionic gating controls the movement of ions with magnetic moments, which induces itinerant ferromagnetism on the surface of Pt films, with large coercivity and perpendicular anisotropy mimicking the ideal two-dimensional Ising-type FM state. The electrical transport of the induced FM state shows Kondo effect at low temperature, suggesting spatially separated coexistence of Kondo scattering beneath the FM interface. The tunable FM state indicates that paramagnetic ionic gating could serve as a versatile method to induce rich transport phenomena combining field effect and magnetism at PIL-gated interfaces.

A Numerical Study of Scalable Cardiac Electro-Mechanical Solvers on HPC Architectures.

We introduce and study some scalable domain decomposition preconditioners for cardiac electro-mechanical 3D simulations on parallel HPC (High Performance Computing) architectures. The electro-mechanical model of the cardiac tissue is composed of four coupled sub-models: (1) the static finite elasticity equations for the transversely isotropic deformation of the cardiac tissue; (2) the active tension model describing the dynamics of the intracellular calcium, cross-bridge binding and myofilament tension; (3) the anisotropic Bidomain model describing the evolution of the intra- and extra-cellular potentials in the deforming cardiac tissue; and (4) the ionic membrane model describing the dynamics of ionic currents, gating variables, ionic concentrations and stretch-activated channels. This strongly coupled electro-mechanical model is discretized in time with a splitting semi-implicit technique and in space with isoparametric finite elements. The resulting scalable parallel solver is based on Multilevel Additive Schwarz preconditioners for the solution of the Bidomain system and on BDDC preconditioned Newton-Krylov solvers for the non-linear finite elasticity system. The results of several 3D parallel simulations show the scalability of both linear and non-linear solvers and their application to the study of both physiological excitation-contraction cardiac dynamics and re-entrant waves in the presence of different mechano-electrical feedbacks.

Gate-Induced Metal–Insulator Transition in MoS2 by Solid Superionic Conductor LaF3

Electric-double-layer (EDL) gating with liquid electrolyte has been a powerful tool widely used to explore emerging interfacial electronic phenomena. Due to the large EDL capacitance, a high carrier density up to 1014 cm-2 can be induced, directly leading to the realization of field-induced insulator to metal (or superconductor) transition. However, the liquid nature of the electrolyte has created technical issues including possible side electrochemical reactions or intercalation, and the potential for huge strain at the interface during cooling. In addition, the liquid coverage of active devices also makes many surface characterizations and in situ measurements challenging. Here, we demonstrate an all solid-state EDL device based on a solid superionic conductor LaF3, which can be used as both a substrate and a fluorine ionic gate dielectric to achieve a wide tunability of carrier density without the issues of strain or electrochemical reactions and can expose the active device surface for external access. Based on LaF3 EDL transistors (EDLTs), we observe the metal-insulator transition in MoS2. Interestingly, the well-defined crystal lattice provides a more uniform potential distribution in the substrate, resulting in less interface electron scattering and therefore a higher mobility in MoS2 transistors. This result shows the powerful gating capability of LaF3 solid electrolyte for new possibilities of novel interfacial electronic phenomena.

Cr doping induced negative transverse magnetoresistance in Cd3As2 thin films

The magnetoresistance of a material conveys various dynamic information about charge and spin carriers, inspiring both fundamental studies in physics and practical applications such as magnetic sensors, data storage, and spintronic devices. Magnetic impurities play a crucial role in the magnetoresistance as they induce exotic states of matter such as the quantum anomalous Hall effect in topological insulators and tunable ferromagnetic phases in dilute magnetic semiconductors. However, magnetically doped topological Dirac semimetals are hitherto lacking. Here, we report a systematic study of Cr-doped $\mathrm{C}{\mathrm{d}}_{3}\mathrm{A}{\mathrm{s}}_{2}$ thin films grown by molecular-beam epitaxy. With the Cr doping, $\mathrm{C}{\mathrm{d}}_{3}\mathrm{A}{\mathrm{s}}_{2}$ thin films exhibit unexpected negative transverse magnetoresistance and strong quantum oscillations, bearing a trivial Berry's phase and an enhanced effective mass. More importantly, with ionic gating the magnetoresistance of Cr-doped $\mathrm{C}{\mathrm{d}}_{3}\mathrm{A}{\mathrm{s}}_{2}$ thin films can be drastically tuned from negative to positive, demonstrating the strong correlation between electrons and the localized spins of the Cr impurities, which we interpret through the formation of magnetic polarons. Such a negative magnetoresistance under perpendicular magnetic field and its gate tunability have not been observed previously in the Dirac semimetal $\mathrm{C}{\mathrm{d}}_{3}\mathrm{A}{\mathrm{s}}_{2}$. The Cr-induced topological phase transition and the formation of magnetic polarons in $\mathrm{C}{\mathrm{d}}_{3}\mathrm{A}{\mathrm{s}}_{2}$ provide insights into the magnetic interaction in Dirac semimetals as well as their potential applications in spintronics.

A Pb2+ ionic gate with enhanced stability and improved sensitivity based on a 4′-aminobenzo-18-crown-6 modified funnel-shaped nanochannel

The existence of heavy ions, such as Pb2+, in the external environment is potentially hazardous as these can be highly toxic to the human body. Inspired by the highly efficient ability of biological ion channels to recognize the metal ion, much effort has been devoted to investigating biomimetic ionic gates based on engineered solid-state conical nanopores/nanochannels. However, the reported system generally displays relatively poor functionality and low stability due to the limited functional region. This article describes an ionic gate with enhanced stability and improved sensitivity based on an emerging advanced funnel-shaped nanochannel system. The ionic gate is developed by anchoring the Pb2+ ion-responsive functional molecules, 4'-aminobenzo-18-crown-6 (4-AB18C6), onto the inner surface of a funnel-shaped polyethylene terephthalate (PET) nanochannel. The system can selectively recognize Pb2+ with an ultra-low concentration of down to approximately 10-15 M and displays excellent stability. The Pb2+ ions will form positively charged complexes through specific association with 4-AB18C6, which would screen the negative charge existing on the channel walls, resulting in a decreased ionic current and also an "OFF state". Since the ability of EDTA to associate with Pb2+ is much stronger than that of 4-AB18C6, the nanochannel can also achieve reversible switching upon the alternating addition of Pb2+ ions and EDTA. The switching behaviors of the system were reflected by the good reproducibility of the tunable rectifying effect. The stability of the conical and funnel-shaped nanochannels is also compared using current scanning under constant voltage. The results have shown that the stability of the funnel-shaped nanochannel is much better than that of the conical nanochannel, and this can be ascribed to its much longer critical region. Consequently, the funnel-shaped nanochannels with enhanced stability and improved sensitivity can potentially be applied in ion transportation, sensors, drug release, and energy conversion.

Ionic Circuits Powered by Reverse Electrodialysis for an Ultimate Iontronic System

Despite numerous reports on iontronic devices, there has been no whole circuit working in aqueous media including even power source. Herein, we introduce complete ionic circuits powered by reverse electrodialysis (RED) for the first time without employing any electronic components. The RED-driven polyelectrolyte diode successfully shows rectification behavior which is verified by monitoring dynamic ion distribution through fluorescence in real-time. We can also turn on and off the voltage applied to the circuit, and apply an arbitrary voltage by precisely manipulating the pressure imposed to an elastic connection tube filled with electrolyte. Furthermore, this new concept containing ionic power source advances to a more sophisticated ionic OR logic gate. The proposed system paves the way to develop not only passive iontronic devices (e.g. current ionic diode), but active ones requiring a source of energy, particularly such as a neuron-like information processor powered by fully ionic systems, and thereby aqueous computers.

Depolarization of the conductance-voltage relationship in the NaV1.5 mutant, E1784K, is due to altered fast inactivation.

E1784K is the most common mixed long QT syndrome/Brugada syndrome mutant in the cardiac voltage-gated sodium channel NaV1.5. E1784K shifts the midpoint of the channel conductance-voltage relationship to more depolarized membrane potentials and accelerates the rate of channel fast inactivation. The depolarizing shift in the midpoint of the conductance curve in E1784K is exacerbated by low extracellular pH. We tested whether the E1784K mutant shifts the channel conductance curve to more depolarized membrane potentials by affecting the channel voltage-sensors. We measured ionic currents and gating currents at pH 7.4 and pH 6.0 in Xenopus laevis oocytes. Contrary to our expectation, the movement of gating charges is shifted to more hyperpolarized membrane potentials by E1784K. Voltage-clamp fluorimetry experiments show that this gating charge shift is due to the movement of the DIVS4 voltage-sensor being shifted to more hyperpolarized membrane potentials. Using a model and experiments on fast inactivation-deficient channels, we show that changes to the rate and voltage-dependence of fast inactivation are sufficient to shift the conductance curve in E1784K. Our results localize the effects of E1784K to DIVS4, and provide novel insight into the role of the DIV-VSD in regulating the voltage-dependencies of activation and fast inactivation.

Structural and electronic phase transitions of MoTe2 induced by Li ionic gating

Monolayer MoTe2 has semiconducting and semimetallic phases with small energy difference, and the relative stability is readily reversed by gating. By first-principles calculations, we investigate the changes in atomic structure, electronic structure, and relative stability of two phases induced by Li ionic gating. To model Li ionic gating, we employ two approaches; one is direct adsorption of Li on MoTe2 and the other is introducing non-contacting Li plate over MoTe2. We show phonon instability in H-phase of MoTe2 with increasing the amount of charge transfer from Li, which implies a large electron-phonon coupling in the system resulting in a charge density wave state. Structural distortion is also observed in highly doped Td phase. The transition energy barrier from distorted H phase to distorted Td phase is reduced considerably compared to that of pristine MoTe2.

(Invited) Investigation of Single WS2 Nanotubes Leads to New Observations and Potential Applications

Multiwall nanotubes and fullerene-like nanoparticles of WS2 are produced in large amounts, offering numerous opportunities for their investigation and future applications. While many studies focus on the preparation and studying the characteristics of bulk matrices incorporating these nanotubes, the investigation of individual nanotubes permits addressing intriguing issues, encompassing their unique optical, electrical and mechanical properties. In this report, the author will dwell on several new studies. FET of WS2 nanotubes with liquid ionic gating demonstrated that the nanotubes become superconducting at low temperatures (5.8 K).1 The magnetoresisitance exhibited strong Little-Parks oscillations under magnetic field parallel to the tube axis, which originates from the interference of the supercurrent along the circumference of the nanotube. The coupling of the supercurrent with the magnetic field in the chiral tubes produces nonreciprocal second harmonic signal. In another study, the electromechanical characteristics of a torsion device based on single nanotube was studied.2 A high frequency resonator with high quality factor was established. The high quality factor of the WS2-based device was attributed to the interlocking of the layers, which minimize the dissipative losses due to reciprocating motion of the nanotubes walls during torsion. The wetting of single WS2 nanotube retracted from a liquid surface was studied experimentally and by detailed computational anlaysis.3 Nanotubes with different diameter and having open or closed tips were studied. It was found that the water does not wet the outer wall of the nanotubes. However, nanotubes with open end of diameter below say 40 nm exhibited strong interaction with the water surface. Careful analyses indicated that strong capillary action leads to the filling of the hollow nanotube core which leads to large dissipated energy during withdrawal of the nanotube. At the end of the talk, the author will briefly deliberate on the commercial applications of fullerene-like WS2 nanoparticles in advanced lubrication and the industrial prospects of nanotubes thereof.

Alternans promotion in cardiac electrophysiology models by delay differential equations.

Cardiac electrical alternans is a state of alternation between long and short action potentials and is frequently associated with harmful cardiac conditions. Different dynamic mechanisms can give rise to alternans; however, many cardiac models based on ordinary differential equations are not able to reproduce this phenomenon. A previous study showed that alternans can be induced by the introduction of delay differential equations (DDEs) in the formulations of the ion channel gating variables of a canine myocyte model. The present work demonstrates that this technique is not model-specific by successfully promoting alternans using DDEs for five cardiac electrophysiology models that describe different types of myocytes, with varying degrees of complexity. By analyzing results across the different models, we observe two potential requirements for alternans promotion via DDEs for ionic gates: (i) the gate must have a significant influence on the action potential duration and (ii) a delay must significantly impair the gate's recovery between consecutive action potentials.

Memory in a fractional-order cardiomyocyte model alters properties of alternans and spontaneous activity

Cardiac memory is the dependence of electrical activity on the prior history of one or more system state variables, including transmembrane potential (Vm), ionic current gating, and ion concentrations. While prior work has represented memory either phenomenologically or with biophysical detail, in this study, we consider an intermediate approach of a minimal three-variable cardiomyocyte model, modified with fractional-order dynamics, i.e., a differential equation of order between 0 and 1, to account for history-dependence. Memory is represented via both capacitive memory, due to fractional-order Vm dynamics, that arises due to non-ideal behavior of membrane capacitance; and ionic current gating memory, due to fractional-order gating variable dynamics, that arises due to gating history-dependence. We perform simulations for varying Vm and gating variable fractional-orders and pacing cycle length and measure action potential duration (APD) and incidence of alternans, loss of capture, and spontaneous activity. In the absence of ionic current gating memory, we find that capacitive memory, i.e., decreased Vm fractional-order, typically shortens APD, suppresses alternans, and decreases the minimum cycle length (MCL) for loss of capture. However, in the presence of ionic current gating memory, capacitive memory can prolong APD, promote alternans, and increase MCL. Further, we find that reduced Vm fractional order (typically less than 0.75) can drive phase 4 depolarizations that promote spontaneous activity. Collectively, our results demonstrate that memory reproduced by a fractional-order model can play a role in alternans formation and pacemaking, and in general, can greatly increase the range of electrophysiological characteristics exhibited by a minimal model.

Brain sodium MRI in human epilepsy: Disturbances of ionic homeostasis reflect the organization of pathological regions

In light of technical advancements supporting exploration of MR signals other than 1H, sodium (23Na) has received attention as a marker of ionic homeostasis and cell viability. Here, we evaluate for the first time the possibility that 23Na-MRI is sensitive to pathological processes occurring in human epilepsy. A normative sample of 27 controls was used to normalize regions of interest (ROIs) from 1424 unique brain locales on quantitative 23Na-MRI and high-resolution 1H-MPRAGE images. ROIs were based on intracerebral electrodes in ten patients undergoing epileptic network mapping. The stereo-EEG gold standard was used to define regions as belonging to primarily epileptogenic, secondarily irritative and to non-involved regions. Estimates of total sodium concentration (TSC) on 23Na-MRI and cerebrospinal fluid (CSF) on 1H imaging were extracted for each patient ROI, and normalized against the same region in controls. ROIs with disproportionate CSF contributions (ZCSF≥1.96) were excluded. TSC levels were found to be elevated in patients relative to controls except in one patient, who suffered non-convulsive seizures during the scan, in whom we found reduced TSC levels. In the remaining patients, an ANOVA (F1100= 12.37, p<0.0001) revealed a highly significant effect of clinically-defined zones (F1100= 11.13, p<0.0001), with higher normalized TSC in the epileptogenic zone relative to both secondarily irritative (F1100= 11, p=0.0009) and non-involved regions (F1100= 17.8, p<0.0001). We provide the first non-invasive, in vivo evidence of a chronic TSC elevation alongside ZCSF levels within the normative range, associated with the epileptogenic region even during the interictal period in human epilepsy, and the possibility of reduced TSC levels due to seizure. In line with modified homeostatic mechanisms in epilepsy – including altered mechanisms underlying ionic gating, clearance and exchange – we provide the first indication of 23Na-MRI as an assay of altered sodium concentrations occurring in epilepsy associated with the organization of clinically relevant divisions of pathological cortex.

Abrupt p-n junction using ionic gating at zero-bias in bilayer graphene

Graphene is a promising candidate for optoelectronic applications. In this report, a double gated bilayer graphene FET has been made using a combination of electrostatic and electrolytic gating in order to form an abrupt p-n junction. The presence of two Dirac peaks in the gating curve of the fabricated device confirms the formation of a p-n junction. At low temperatures, when the electrolyte is frozen intentionally, the photovoltage exhibits a six-fold pattern indicative of the hot electron induced photothermoelectric effect that has also been seen in graphene p-n junctions made using metallic gates. We have observed that the photovoltage increases with decreasing temperature indicating a dominant role of supercollision scattering. Our technique can also be extended to other 2D materials and to finer features that will lead to p-n junctions which span a large area, like a superlattice, that can generate a larger photoresponse. Our work creating abrupt p-n junctions is distinct from previous works that use a source–drain bias voltage with a single ionic gate creating a spatially graded p-n junction.

Long-Range Lattice Engineering of MoTe2 by a 2D Electride.

Doping two-dimensional (2D) semiconductors beyond their degenerate levels provides the opportunity to investigate extreme carrier density-driven superconductivity and phase transition in 2D systems. Chemical functionalization and the ionic gating have achieved the high doping density, but their effective ranges have been limited to ∼1 nm, which restricts the use of highly doped 2D semiconductors. Here, we report on electron diffusion from the 2D electride [Ca2N]+·e- to MoTe2 over a distance of 100 nm from the contact interface, generating an electron doping density higher than 1.6 × 1014 cm-2 and a lattice symmetry change of MoTe2 as a consequence of the extreme doping. The long-range lattice symmetry change, suggesting a length scale surpassing the depletion width of conventional metal-semiconductor junctions, was a consequence of the low work function (2.6 eV) with highly mobile anionic electron layers of [Ca2N]+·e-. The combination of 2D electrides and layered materials yields a novel material design in terms of doping and lattice engineering.

Design of Multifunctional Nanogate in Response to Multiple External Stimuli Using Amphiphilic Diblock Copolymer.

Nature uses the interplay between hydrophobic and electrostatic interactions of disordered proteins to orchestrate complicated molecular gates such as the nuclear pore complex to control the transport of biological masses. Inspired by nature, we here theoretically show that well-defined gate shape, sensitive response to pH and salt concentration, and selectivity in cargo transport can be simultaneously achieved by grafting amphiphilic diblock copolymers made of sequence-controlled hydrophobic and ionizable monomers on the inner surface of solid-state nanopore. As a result, multiple functions such as ionic gating and molecular filtering can be implemented into one single copolymer nanogate. The gate structure and thermodynamics is a result of the self-assembly of the sequence-designed copolymer in the confined geometry that minimizes the free energy of the system. Our theory further predicts a phase transition and discontinuous charge regulation of the confined copolymer that allows logical gating in biosensors and nanofluidic devices. As an example of application, a nanolocker with the potential of molecular pumping has also been designed with the cooperation of two amphiphilic copolymer gates. Our results highlight the importance of polymer sequence in nanogating, and these insights can be used to guide the rational design of polymer-coated smart nanopores.