Electrically induced directional ion migration in two-dimensional perovskite heterostructures
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2D halide perovskite↗
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Non-equilibrium insertion of lithium ions into graphite
Graphite has been regarded as the most important anode material for currently used lithium-ion batteries due to its two-dimensional (2D) nature hosting ionic intercalations. However, the kinetic insertion of Li ions is still not well known microscopically. In this work, we investigate the real-time intercalation process of Li ions using in situ transmission electron microscopy. We observe the lithium insertion process at the atomic scale, in which the graphite layers undergo expansion, forming wrinkles and finally inhomogeneous cracks as the Li ions accumulate, different from the proposed models. Leveraging on theoretical simulations, Li-ion migration driven by an external electrical field is suggested to be induced into the irreversible wrinkled structures. This non-equilibrium behavior that occur in lithium-ion batteries can be more pronounced at a high charging rate, which will practically degrade the capacity of graphite. Furthermore, this work unveils the reaction scenario of the non-equilibrium Li-ion insertion, which benefits the understanding of the performance of graphite-based energy-storage devices.
25 ENERGY STORAGE↗
Ionic diffusioosmotic transport in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory
In this paper, we study the diffusioosmotic (DOS) transport in a nanochannel grafted with pH-responsive polyelectrolyte (PE) brushes and establish brush-functionalization-driven enhancement in induced nanofluidic electric field and electrokinetic transport. The PE brushes are modelled using our recently developed augmented strong stretching theory (SST). We consider the generation of the DOS transport due to the imposition of a salt concentration gradient along the length of the nanochannel. The presence of the salt concentration gradient induces an electric field that has an osmotic (associated with the flow-driven migration of the ions in the induced electric double layer) and an ionic (associated with the conduction current) component. These two components evolve in a manner such that the electric field in the brush-grafted nanochannel is larger (smaller) in magnitude than that in the brush-less nanochannels for the case where the electric field is positive (negative). Furthermore, we quantify the DOS flow velocity and establish that for most of the parameter choices, the DOS velocity, which is a combination of the induced pressure-gradient-driven chemiosmotic component and the induced electric field driven electroosmotic transport, is significantly larger for the nanochannels grafted with backbone-charged PE brushes (i.e., brushes where the charge is distributed along the entire length of the brushes) as compared to brush-free nanochannels or nanochannels grafted with PE brushes containing charges on their non-grafted ends.
42 ENGINEERING↗
Local p‐ and n‐Type Doping of an Oxide Semiconductor via Electric‐Field‐Driven Defect Migration
Layered oxides exhibit high ionic mobility and chemical flexibility, attracting interest as cathode materials for lithium-ion batteries and the pairing of hydrogen production and carbon capture. Recently, layered oxides emerged as highly tunable semiconductors. For example, by introducing anti-Frenkel defects, the electronic hopping conductance in hexagonal manganites is increased locally by orders of magnitude. Here, local acceptor and donor doping in Er(Mn,Ti)O3 is demonstrated, facilitated by the controlled splitting of anti-Frenkel defects under applied d.c. voltage. By combining density functional theory calculations, scanning probe microscopy, atom probe tomography, and scanning transmission electron microscopy, it is shown that the oxygen defects can readily be moved through the layered crystal structure, leading to nano-sized interstitial-rich (p-type) and vacancy-rich (n-type) regions. The resulting pattern is comparable to dipolar npn-junctions and stable on the timescale of days. These findings reveal the possibility of temporarily functionalizing oxide semiconductors at the nanoscale, giving additional opportunities for the field of oxide electronics and the development of transient electronics in general.
He, Jiali↗
Electrically-driven IMT and volatile memristor behavior in NdNiO 3 films
Abstract Transition metal oxides with insulator-metal transitions (IMTs) are uniquely suited for volatile memristor devices that mimic the spiking of biological neurons. Unlike most non-volatile memristors, which often operate via ion migration into filaments, volatile devices utilize a reversible phase change that returns to a ground state in the absence of applied stimulus. In these devices, Joule heating triggers the IMT and changes the bulk resistivity rather than influencing conduction through defects, as in previous studies. This volatile resistive switching behavior has previous been leveraged in niobium and vanadium oxides, but not in rare-earth nickelates, despite their tunable transition temperatures. This study demonstrates an electrically driven IMT in the prototypical rare-earth nickelate, NdNiO 3 , in large area devices. While previous work examining the electrically-driven IMT in NdNiO 3 suggests defect-dominated conduction, this study shows clear s-type negative differential resistance (NDR) consistent with temperature-dependent resistivity measurements. The NDR peak-to-valley voltage scales linearly with temperature as expected for conductivity pathways dominated by bulk IMT behavior. Unlike other transition metal oxides, which are modeled using the insulator-metal phase fraction as the internal state variable, a thermoelectric model with temperature as the internal state variable is found to more accurately describe the current–voltage characteristic of NdNiO 3 volatile memristors. Overall, we report the synthesis, fabrication, and characterization of NdNiO 3 volatile memristors with resistivity dominated by bulk-like IMT behavior which is scalable and not dependent upon oxygen vacancy migration or defect mediated conduction pathways.
36 MATERIALS SCIENCE↗
Cation Crossover Limits Accessible Current Densities for Zero-Gap Alkaline CO2 Reduction to Ethylene
Traditional CO2 reduction systems often fail in an alkaline environment due to the interaction of CO2 with a high-pH electrolyte, where carbonate and bicarbonate ion formation results in potassium-containing salt precipitation. The presence of the salt crystals causes a reduction in the selectivity of the electrolyzer toward CO2 conversion. Here, the critical operational variables, which elicit the salting out process, are investigated (i.e., ion transport). When the electrolyzer exceeds a critical current density, H2 evolution dominates CO2 reduction due to salt formation, which is confirmed by postmortem cross-sectional SEM-EDS of the electrode. The critical current density decreases with an increasing membrane thickness or anolyte ionic strength. Cathode salt formation is mediated by the unmitigated crossover of cations from the anolyte to the cathode across an anion exchange membrane, through which cations are imperfectly excluded. It is likely that electric field-driven migration promotes an increase in concentration of potassium across the membrane, until, at the critical current density for that electrolyzer arrangement, the concentration of potassium and bicarbonate ions exceeds the solubility limit of KHCO3, leading to salt precipitation.
CO2 reduction↗
Low Threshold Voltages Electrochemically Drive Gold Migration in Halide Perovskite Devices
The constituent ions of halide perovskite materials are mobile in the solid state and known to participate in reduction/oxidation reactions. Yet few parameters related to electrochemical processes occurring within devices have been carefully determined. Here, we characterize such reactions in model MAPbI3 perovskite devices, and we quantify threshold voltages for key reactions. Gold is oxidized and mobilized under nitrogen, in the dark, at the MAPbI3/Au interface at 0.8 V. When this interface is buffered with the organic hole transport material (HTM), 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamino)-9,9'-spirobifluorene, MAPbI3 begins to degrade at 1.2 V; degradation liberates ions that subsequently enable Au migration. Thresholds are insensitive to MAPbI3 thickness or choice of organic HTM or oxide cathode, which suggests that these reactions are driven electrochemically; the electric field across the device is less important. These results have profound implications for understanding in operando degradation pathways of optoelectronic perovskite devices that are varied in terms of interface structures, active material compositions, and ranges of external stressors.
42 ENGINEERING↗
Solid-State Ionic Rectification in Perovskite Nanowire Heterostructures
Halide perovskites have attracted increasing research attention with regard to their potential for optoelectronic applications. Because of its low activation energy, ion migration is implicated in the long-term stability and many unusual transport behaviors of halide perovskite devices. However, direct observation and precise control of the ionic transport in halide perovskite crystals remain challenging. Here, we have designed an axial CsPbBr 3 -CsPbCl 3 nanowire heterostructure, in which electric-field-induced halide ion migration was clearly visualized and quantified. We demonstrated that halide ion migration is dependent on the applied electric field and exhibits ionic rectification in this solid-state system, which is due to the nonuniform distribution of the ionic vacancies in the nanowire that results from a competition between electrical screening and their creation/destruction at the electrodes' interfaces. Furthermore, the asymmetric heterostructure characteristics add an additional knob to control the ion movement in the design of advanced ionic circuits with halide perovskites as building blocks.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Mitigating electrochemical degradation in CsPbBr{sub 3} gamma detectors by organic and inorganic encapsulation.
CsPbBr3 perovskite semiconductors have emerged as a leading candidate for nextgeneration radiation detectors because of their exceptional charge transport properties, defect tolerance, and record-breaking sensitivity and energy resolution. Their long-term stability, however, is hindered by electrode-driven electrochemical decomposition, which is accelerated by moisture- and oxygen-assisted ion migration during operation. Here, we investigated organic and inorganic encapsulation strategies as both environmental barriers and means to suppress interfacial degradation pathways. Atomic layer deposition (ALD) of Al2O3 provided a conformal passivation layer that blocked environmental ingress, suppressed ionic diffusion, reduced leakage current, enhanced energy resolution and expanded the operational electric-field window beyond 5 kV∙cm1 . By contrast, organic encapsulants such as paraffin wax and polystyrene slowed moisture diffusion but did not suppress interfacial reactions, with wax extending stability to over 90 days. These results show that ALD-Al2O3 suppresses dominant interfacial degradation pathways, enabling stable, high-field operation and advancing the practical deployment of CsPbBr3 γ-ray detectors.
Unal, Mustafa↗
Selective Ion Enrichment and Charge Storage through Transport Hysteresis in Conical Nanopipettes
Greater selectivity and controls in the ion transport dynamics are essential in fields such as charge storage, separation, energy storage and conversion, neuromorphic computing and learning, electrochemistry, to name a few. Mechanistic insights into the intriguing hysteresis effects in the rectified electrokinetic transport through single conical nanopipettes are unveiled by combining time-resolved electroanalytical experiments with numeric simulation. Cations as counterions for surface charges are found to dominate not just the through-nanopore flux but also the hysteresis charges, that is, the net enriched or expelled charges during the transport process. Built on our earlier report on the through-nanopore ion flux dominated by counterions for surface charges, the “trapped ions” or hysteresis charges are analyzed herein. Cation selectivity is almost 100% in the hysteresis charges during the potential scans in low conductivity states driven by the combined applied and intrinsic surface electrical fields. Surprisingly, the cation selectivity in the total hysteresis charges remains high at 70–80% over a wide bulk concentration range in the high conductivity (HC) states, where higher ionic strength due to ion enrichment would decrease electrostatistic effects and thus ion selectivity. The retained high selectivity at HC is explained by the competition effects of electroosmotic flow against the co-ion migration. Furthermore, the respective cation and anion portions in the total hysteresis charges over a wide range of ionic strength and measurement conditions provide generalizable strategies for improvements in both transport throughput and selectivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Direct Visualization of Charge Migration in Bilayer Tantalum Oxide Films by Multimodal Imaging
Inspired by biological neuromorphic computing, artificial neural networks based on crossbar arrays of bilayer tantalum oxide memristors have shown to be promising alternatives to conventional complementary metal-oxide-semiconductor (CMOS) architectures. In order to understand the driving mechanism in these oxide systems, tantalum oxide films are resistively switched by conductive atomic force microscopy (C-AFM), and subsequently imaged by kelvin probe force microscopy (KPFM) and spatially resolved time-of-flight secondary ion mass spectrometry (ToF-SIMS). These workflows enable induction and analysis of the resistive switching mechanism as well as control over the resistively switched region of the film. In this work it is shown that the resistive switching mechanism is driven by both current and electric field effects. Reversible oxygen motion is enabled by applying low (<1 V) electric fields, while high electric fields generate irreversible breakdown of the material (>1 V). Fully understanding oxygen motion and electrical effects in bilayer oxide memristor systems is a fundamental step toward the adoption of memristors as a neuromorphic computing technology.
36 MATERIALS SCIENCE↗
Lead-Free Organic–Perovskite Hybrid Quantum Wells for Highly Stable Light-Emitting Diodes
Two-dimensional perovskites that could be regarded as natural organic-inorganic hybrid quantum wells (HQWs) are promising for light-emitting diode (LED) applications. High photoluminescence quantum efficiencies (approaching 80%) and extremely narrow emission bandwidth (less than 20 nm) have been demonstrated in their single crystals; however, a reliable electrically driven LED device has not been realized owing to inefficient charge injection and extremely poor stability. Furthermore, the use of toxic lead raises concerns. Here, we report Sn(II)-based organic-perovskite HQWs employing molecularly tailored organic semiconducting barrier layers for efficient and stable LEDs. Utilizing femtosecond transient absorption spectroscopy, we demonstrate the energy transfer from organic barrier to inorganic perovskite emitter occurs faster than the intramolecular charge transfer in the organic layer. Consequently, this process allows efficient conversion of lower-energy emission associated with the organic layer into higher-energy emission from the perovskite layer. Thus, this greatly broadened the candidate pool for the organic layer. Incorporating a bulky small bandgap organic barrier in the HQW, charge transport is enhanced and ion migration is greatly suppressed. We demonstrate a HQW-LED device with pure red emission, a maximum luminance of 3466 cd m -2 , a peak external quantum efficiency up to 3.33%, and an operational stability of over 150 h, which are significantly better than previously reported lead-free perovskite LEDs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tunable stochastic memristors for energy-efficient encryption and computing
Information security and computing, two critical technological challenges for post-digital computation, pose opposing requirements – security (encryption) requires a source of unpredictability, while computing generally requires predictability. Each of these contrasting requirements presently necessitates distinct conventional Si-based hardware units with power-hungry overheads. This work demonstrates Cu 0.3 Te 0.7 /HfO 2 (‘CuTeHO’) ion-migration-driven memristors that satisfy the contrasting requirements. Under specific operating biases, CuTeHO memristors generate truly random and physically unclonable functions, while under other biases, they perform universal Boolean logic. Using these computing primitives, this work experimentally demonstrates a single system that performs cryptographic key generation, universal Boolean logic operations, and encryption/decryption. Circuit-based calculations reveal the energy and latency advantages of the CuTeHO memristors in these operations. This work illustrates the functional flexibility of memristors in implementing operations with varying component-level requirements.
97 MATHEMATICS AND COMPUTING↗
Simultaneous Energy Generation and Flow Enhancement (Electroslippage Effect) in Polyelectrolyte Brush Functionalized Nanochannels
Energy generation through nanofluidics is a topic of great nanotechnological relevance. In this work, we conduct all-atom molecular dynamics (MD) simulations of the transport of water and ions in a pressure-driven flow in nanochannels grafted with charged polyelectrolyte (PE) brushes and discover the possibility of simultaneous electrokinetic energy generation and flow enhancement (henceforth denoted as the electroslippage effect). Such PE-brush-functionalized nanochannels have been recently shown to demonstrate an overscreening (OS) effect (characterized by the presence of a greater number of screening counterions within the PE brush layer than needed to screen the PE brush charges), a consequent presence of excess coions within the PE brush-free bulk, and a coion-driven electroosmotic (EOS) transport in the presence of small to moderate applied axial electric fields. Here, however, we find that the streaming current, which represents the current generated by the flow-driven downstream advection of the charge imbalance present within the electric double layer (EDL) that screen the PE brush charges, is governed by the migration of the counterions. This stems from the fact that the highest contribution to the overall streaming current arises from the region near the PE brush-water interface (where there is an excess of counterions), while the brush-free bulk yields a hitherto unreported, but small, coion-dictated streaming current. This downstream advection of the charge imbalance (and the resultant counterion-driven streaming current) eventually leads to the development of an electric field (streaming electric field) in the direction that is opposite to the direction of the counterion-driven streaming current. The streaming current and the streaming electric field interact to generate the electrokinetic energy. Equally importantly, this streaming electric field induces an EOS transport, which becomes coion-driven, due to the presence of excess coions in the brush-free bulk. For the case of nanochannels grafted with negatively charged PE brushes, the streaming electric field will be in a direction that is opposite to the pressure-driven transport, and hence the coion (or anion) driven EOS flow, will be in the same direction as the pressure-driven transport. On the other hand, for the case of nanochannels grafted with positively charged PE brushes, the streaming electric field will be in the same direction as the pressure-driven flow, and hence the coion (or cation) driven EOS flow, will again be in the same direction as the pressure-driven flow. Therefore, whenever there occurs the presence of the OS and the resulting coion-driven EOS transport in PE brush grafted nanochannels, regardless of the sign of the charges of the PE brushes, this EOS transport will always aid the pressure-driven transport and will cause the most fascinating increase in the net volume flow rate across the nanochannel cross section, which is the electroslippage effect.
overscreening↗
Interfacial-Redox-Induced Tuning of Superconductivity in YBa 2 Cu 3 O 7-δ
Solid-state ionic approaches for modifying ion distributions in getter/oxide heterostructures offer exciting potentials to control material properties. Here, we report a simple, scalable approach allowing for manipulation of the superconducting transition in optimally doped YBa 2 Cu 3 O 7-δ (YBCO) films via a chemically driven ionic migration mechanism. Using a thin Gd capping layer of up to 20 nm deposited onto 100 nm thick epitaxial YBCO films, oxygen is found to leach from deep within the YBCO. Progressive reduction of the superconducting transition is observed, with complete suppression possible for a sufficiently thick Gd layer. These effects arise from the combined impact of redox-driven electron doping and modification of the YBCO microstructure due to oxygen migration and depletion. Finaly, this work demonstrates an effective step toward total ionic tuning of superconductivity in oxides, an interface-induced effect that goes well into the quasi-bulk regime, opening-up possibilities for electric field manipulation.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Interpretation of large‐scale, long‐term electrical geophysical monitoring guided by a process simulation
Abstract Surface electrical resistivity tomography (ERT) was used at a waste site to monitor vadose zone changes in electrical properties as a proxy for contaminant flux over a span of 17 years. The BC Cribs and Trenches (BCCT) site at the Hanford site contains 20 disposal trenches and six disposal cribs. Wastes include a large inventory of technetium‐99 and large masses of nitrate and uranium‐238. ERT data were collected along 41 profiles in 2005 to characterize regions of elevated bulk electrical conductivity (BEC) associated with past liquid waste discharges. Previous analyses performed on samples from four boreholes showed a high correlation between nitrate concentration and BEC. In 2022, ERT data were re‐collected along the same profiles and six additional profiles in an area not previously surveyed. Compared to background uncontaminated areas, BEC was higher in contaminated areas at the waste sites. Given the correlation between nitrate concentration and BEC previously found at this site, ERT images show the spatial distribution and relative ionic concentration of vadose zone contaminants at BCCT. Between 2005 and 2022, ERT difference images showed a decrease in BEC surrounding most waste sites, with exceptions where there were known anthropogenic surface changes. An evaluation of recharge‐driven nitrate migration using synthetic flow and transport simulations showed that downward migration causes a decrease in BEC from the decrease in ionic strength at the trailing end of the plume where contaminants migrated downward. From this, we interpret ERT difference images as showing the predominant regions of downward ion flux.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗