Continuous Control of Charge Transport in Bi‐Deficient BiFeO3 Films Through Local Ferroelectric Switching

It is demonstrated that electric transport in Bi‐deficient Bi_1‐δFeO₃ ferroelectric thin films, which act as a p‐type semiconductor, can be continuously and reversibly controlled by manipulating ferroelectric domains. Ferroelectric domain configuration is modified by applying a weak voltage stress to Pt/Bi_1‐δFeO₃/SrRuO₃ thin‐film capacitors. This results in diode behavior in macroscopic charge‐transport properties as well as shrinkage of polarization‐voltage hysteresis loops. The forward current density depends on the voltage stress time controlling the domain configuration in the Bi_1‐δFeO₃ film. Piezoresponse force microscopy shows that the density of head‐to‐head/tail‐to‐tail unpenetrating local domains created by the voltage stress is directly related to the continuous modification of the charge transport and the diode effect. The control of charge transport is discussed in conjunction with polarization‐dependent interfacial barriers and charge trapping at the non‐neutral domain walls of unpenetrating tail‐to‐tail domains. Because domain walls in Bi_1‐δFeO₃ act as local conducting paths for charge transport, the domain‐wall‐mediated charge transport can be extended to ferroelectric resistive nonvolatile memories and nanochannel field‐effect transistors with high performances conceptually.     

Hierarchical Domain Structure and Extremely Large Wall Current in Epitaxial BiFeO3 Thin Films

Erasable electrical conductive domain walls in an insulating ferroelectric matrix provide novel functionalities for applications in logic and memory devices. The crux of such success requires sufficiently high wall currents to drive high‐speed and high‐power nanodevices. This work provides an appealing strategy to increase the current by two orders of magnitude through the careful selection of current flowing paths along the charged walls. The dense walls come into form through the hierarchical evolution of the 71°, 109°, and 180° domains of epitaxial BiFeO₃ films in a planar‐geometry ferroelectric resistance‐switching memory cell. The engineered films grown on SrTiO₃ and GdScO₃ substrates allow the observation of detailed local configurations and the evolution of the different domain types using vector piezo‐force microscopy. The higher local electrical conductivity near the charged domain walls is identified by conductive atomic‐force microscopy. It is shown that 180° domain reversal proceeds by three‐step 71° rotations of the pristine domains. Surprisingly, a maximum current of ≈300 nA is observed for current paths along charge‐uncompensated head‐to‐head hierarchical domain walls connecting the two electrodes on the film surface. Furthermore, the achievable current level can be conveniently controlled by varying the relative directions of the initial polarization and the applied field.     

Manipulation of Conductive Domain Walls in Confined Ferroelectric Nanoislands

Conductive ferroelectric domain walls—ultranarrow configurable conduction paths—have been considered as essential building blocks for future programmable domain wall electronics. For applications in high‐density devices, it is imperative to explore the conductive domain walls in small confined systems, while earlier investigations have hitherto focused on thin films or bulk single. Here, an observation and manipulation of conductive domain walls confined within small BiFeO₃ nanoislands aligned in high‐density arrays are demonstrated. Using conductive atomic force microscopy, various types of conductive domain walls, including the head‐to‐head charged domain walls (CDWs), zigzag domain walls, and typical 71° head‐to‐tail neutral domain walls (NDWs), are distinctly visualized. The CDWs exhibit remarkably enhanced metallic conductivity with current of ≈nA order in magnitude and 10⁴ times larger than that inside domains (0.01–0.1 pA), while the semiconducting NDWs allow much smaller current (≈10 pA) than the CDWs. The substantial difference in conductivity for dissimilar walls enables manipulations of various wall conduction states for individual addressable nanoislands via electrical tuning of domain structures. A controllable writing of four distinctive states in individual nanoislands can be achieved, showing application potentials for developing multilevel high‐density memories.     

Conformational Domain Wall Switch

Domain walls in ferroelectric materials have tantalizing potential in disruptive memory and reconfigurable nanoelectronics technologies. Here, a ferroelectric domain wall switch with three distinct addressable resistance states is demonstrated. The device operation hinges on fully controllable and reversible conformational changes of the domain wall. As validated by atomistic simulations consistent with the experiments, using electric field, the shape—and hence the charge state—of the domain wall and ultimately its conduction are altered. Sequential nanoscale transitions of the walls are visualized directly using stroboscopic‐piezoresponse force microscopy and Kelvin probe microscopy. Anisotropic head‐to‐head domain wall injection, stabilized by the majority carrier type of the ferroelectric, BiFeO₃, is identified as the key factor that enables conformational control.     

Giant Domain Wall Conductivity in Self-Assembled BiFeO3 Nanocrystals

Ever-increasing demand on electronic devices with ultrahigh-density non-volatile data storage has attracted great interest in novel ferroelectric memories based on conductive ferroelectric domain walls. Embedded in an insulating material, ferroelectric domain walls have the capability of being (re)created, displaced, erased, and altered in their spatial configurations and electronic characteristics. However, the domain wall conductivities are in most cases not yet sufficiently high to ensure the current density required to drive read-out circuits operating at high speeds. In this work, a giant domain wall current (>10 µA) of a single charged domain wall is obtained through conductive atomic force microscopy with a bias field of 4 V. This is achieved in self-assembled BiFeO₃ nanocrystals grown by sol-gel method on Nb-doped SrTiO₃ substrates. Local configurations of domains and domain wall types are studied using vector piezoresponse force microscopy and high-resolution transmission electronic microscopy. The enhancement of the wall current is shown to be due to the formation of conducting pathways of charged defects accumulated along domain walls and traversing the nanocrystals. The diverse domain walls can be manipulated by electric field in a perpendicular architecture. The perpendicular array structure of BiFeO₃ nanocrystals should have great potentials for developing perpendicular nanoelectronic prototypes.     

Direct Observation of Ferroelectric Domain Walls in LiNbO3: Wall‐Meanders,Kinks, and Local Electric Charges

Direct observations of the ferroelectric domain boundaries in LiNbO₃ are performed using high‐resolution high‐angle annular dark field scanning transmission electron microscopy imaging, revealing a very narrow width of the domain wall between the 180° domains. The domain walls demonstrate local side‐way meandering, which results in inclinations even when the overall wall orientation follows the ferroelectric polarization. These local meanders contain kinks with “head‐to‐head” and “tail‐to‐tail” dipolar configurations and are therefore locally charged. The charged meanders are confined to a few cation layers along the polarization direction and are separated by longer stretches of straight domain walls.     

Observation of Unconventional Dynamics of Domain Walls in Uniaxial Ferroelectric Lead Germanate

Application of scanning probe microscopy techniques such as piezoresponse force microscopy (PFM) opens the possibility to re‐visit the ferroelectrics previously studied by the macroscopic electrical testing methods and establish a link between their local nanoscale characteristics and integral response. The nanoscale PFM studies and phase field modeling of the static and dynamic behavior of the domain structure in the well‐known ferroelectric material lead germanate, Pb₅Ge₃O₁₁, are reported. Several unusual phenomena are revealed: 1) domain formation during the paraelectric‐to‐ferroelectric phase transition, which exhibits an atypical cooling rate dependence; 2) unexpected electrically induced formation of the oblate domains due to the preferential domain walls motion in the directions perpendicular to the polar axis, contrary to the typical domain growth behavior observed so far; 3) absence of the bound charges at the 180° head‐to‐head (H–H) and tail‐totail (T–T) domain walls, which typically exhibit a significant charge density in other ferroelectrics due to the polarization discontinuity. This strikingly different behavior is rationalized by the phase field modeling of the dynamics of uncharged H–H and T–T domain walls. The results provide a new insight into the emergent physics of the ferroelectric domain boundaries, revealing unusual properties not exhibited by conventional Ising‐type walls.     

Truly Electroforming‐Free and Low‐Energy Memristors with Preconditioned Conductive Tunneling Paths

1S1R (1 selector and 1 memristor) is a laterally scalable and vertically stackable scheme that can lead to the ultimate memristor density for either memory or neural network applications. In such a scheme, the memristor device needs to be truly electroforming‐free and operated at both low currents and low voltages in order to be compatible with a two‐terminal selector. In this work, a new type of memristor with a preconditioned tunneling conductive path is developed to achieve the required performance characteristics, including truly electroforming‐free, low current below 30 µA (potentially <1 µA), and simultaneously low voltage ≈±0.7 V in switching operations. Such memristors are further integrated with two types of recently developed selectors to demonstrate the feasibility of 1S1R integration.     

Memristor Kinetics and Diffusion Characteristics for Mixed Anionic‐Electronic SrTiO3‐δ Bits: The Memristor‐Based Cottrell Analysis Connecting Material to Device Performance

Memristors based on mixed anionic‐electronic conducting oxides are promising devices for future data storage and information technology with applications such as non‐volatile memory or neuromorphic computing. Unlike transistors solely operating on electronic carriers, these memristors rely, in their switch characteristics, on defect kinetics of both oxygen vacancies and electronic carriers through a valence change mechanism. Here, Pt|SrTiO_3‐δ|Pt structures are fabricated as a model material in terms of its mixed defects which show stable resistive switching. To date, experimental proof for memristance is characterized in hysteretic current–voltage profiles; however, the mixed anionic‐electronic defect kinetics that can describe the material characteristics in the dynamic resistive switching are still missing. It is shown that chronoamperometry and bias‐dependent resistive measurements are powerful methods to gain complimentary insights into material‐dependent diffusion characteristics of memristors. For example, capacitive, memristive and limiting currents towards the equilibrium state can successfully be separated. The memristor‐based Cottrell analysis is proposed to study diffusion kinetics for mixed conducting memristor materials. It is found that oxygen diffusion coefficients increase up to 3 × 10^–15 m²s^–1 for applied bias up to 3.8 V for SrTiO_3‐δ memristors. These newly accessible diffusion characteristics allow for improving materials and implicate field strength requirements to optimize operation towards enhanced performance metrics for valence change memristors.     

Electronic Synapses Enabled by an Epitaxial SrTiO3-δ / Hf0.5Zr0.5O2 Ferroelectric Field-Effect Memristor Integrated on Silicon

Synapses play a vital role in information processing, learning, and memory formation in the brain. By emulating the behavior of biological synapses, electronic synaptic devices hold the promise of enabling high-performance, energy-efficient, and scalable neuromorphic computing. Ferroelectric memristive devices integrate the characteristics of both ferroelectric and memristive materials and present a far-reaching potential as artificial synapses. Here, it is reported on a new ferroelectric device on silicon, a field-effect memristor, consisting of an epitaxial ultrathin ferroelectric Hf_0.5Zr_0.5O₂ film sandwiched between an epitaxial highly doped oxide semiconductor SrTiO_3-δ and a top metal. Upon a low voltage of less than 2 V, the field-effect modulation in the semiconductor enables to access multiple states. The device works in a large time domain ranging from milliseconds down to tens of nanoseconds. By gradually switching the polarization by identical pulses, the ferroelectric diode devices can dynamically adjust the synaptic strength to mimic short- and long-term memory plasticity. Ionic contributions due to redox processes in the oxide semiconductor beneficially influence the device operation and retention.     

Printable Ferroelectric PVDF/PMMA Blend Films with Ultralow Roughness for Low Voltage Non‐Volatile Polymer Memory

Here, a facile route to fabricate thin ferroelectric poly(vinylidene fluoride) (PVDF)/poly(methylmethacrylate) (PMMA) blend films with very low surface roughness based on spin‐coating and subsequent melt‐quenching is described. Amorphous PMMA in a blend film effectively retards the rapid crystallization of PVDF upon quenching, giving rise to a thin and flat ferroelectric film with nanometer scale β‐type PVDF crystals. The still, flat interfaces of the blend film with metal electrode and/or an organic semi‐conducting channel layer enable fabrication of a highly reliable ferroelectric capacitor and transistor memory unit operating at voltages as low as 15 V. For instance, with a TIPS‐pentacene single crystal as an active semi‐conducting layer, a flexible ferroelectric field effect transistor shows a clockwise I–V hysteresis with a drain current bistability of 10³ and data retention time of more than 15 h at ±15 V gate voltage. Furthermore, the robust interfacial homogeneity of the ferroelectric film is highly beneficial for transfer printing in which arrays of metal/ferroelectric/metal micro‐capacitors are developed over a large area with well defined edge sharpness.     

Intrinsic Mechanical Compliance of 90° Domain Walls in PbTiO3

Functionality of domain walls and other topological defects in ferroelectrics is being widely investigated for applications in electronic devices. While the intrinsic electronic properties of a wall have been considered, its inherent mechanical properties remain explored very little, despite the fact that coupling between strain and polarization is prevalent in many of these materials. Herein, an in-depth study of variations in nanomechanical properties at 90^o domain walls and their adjacent domains in single-crystalline lead titanate (PbTiO₃) is presented as a prototypical ferroelectric material using a combination of various atomic force microscopy (AFM)-based methods. Considerable variations of elastic moduli are found at 90^o domain walls extending up to ~100 nm into the domain areas. AFM nanoindentation also allows to extract local domain wall hardness and plastic and elastic deformation energies. These findings have implications for the design of ferroelectric domain wall functionality that incorporates the intrinsic elastic compliance of a domain wall.     

Simulations of electric field domain suppression in a superlattice oscillator device using a distributed circuit model

We present a method for simulating static domain formation in distributed negative differential resistance devices using a distributed circuit array model coupled with quantum transport simulations. This simulation method is applied to the case of a superlattice Bloch oscillator to ascertain the efficacy of electric field domain wall suppression by micro shunt side walls. Two independent simulation mechanisms using the same basic distributed circuit model are employed to separate simulation artifacts from true physical trends. Simulations are presented, suggesting that the presence of the micro shunt can suppress domain formation above a critical device bias voltage. The simulated dependence of this critical voltage on macroscopic device parameters is presented.     

Nano‐Domain Pinning in Ferroelastic‐Ferroelectrics by Extended Structural Defects

Most ferroelectrics are also ferroelastics (hysteretic stress‐strain relationship and response to mechanical stresses). The interactions between ferroelastic twin walls and ferroelectric domain walls are complex and only partly understood, hindering the technological potential of these materials. Here we study via atomic force microscopy the pinning of 180‐degree ferroelectric domain walls in lead zirconate titanate (PZT). Our observations satisfy all three categories of ferroelectric‐ferroelastic domain interaction proposed by Bornarel, Lajzerowicz, and Legrand.     

Origin of Grain Size Effects on Voltage‐Driven Ferroelastic Domain Evolution in Polycrystalline Tetragonal Lead Zirconate Titanate Thin Film

Grain size effects on electromechanical properties and voltage‐driven ferroelastic domain wall motion are a well‐known phenomenon in polycrystalline ferroelectrics. Here, the origin of the grain size effects on voltage‐driven ferroelastic domain wall motion is presented with the direct observation of ferroelastic domain evolution with applied DC voltage by piezoelectric force microscopy and polarization hysteresis loop. It is demonstrated that the microstructure parameter for controlling the voltage‐driven ferroelastic domain wall motion is the number of colonies of stripe domains in a grain rather than the grain size. Single colony grains do not show considerable out‐of‐plane (001) domain width change whereas multiple colony grains exhibit significant domain width increase with an applied DC voltage. No independent grain size effect on ferroelastic domain wall motion is observed in the grain size range 0.6–1.6 µm.     

Photoassisted Electroforming Method for Reliable Low‐Power Organic–Inorganic Perovskite Memristors

Organic–inorganic hybrid perovskite memristors with high resistive‐switching (RS) reliability and low power consumption are crucial for high‐density storage and high‐efficiency neuromorphic computing. However, the current overshoot in the electroforming process generally induces overgrowth of conductive filaments (CFs) and degrades the RS performance. Here, a simple photo‐assisted electroforming (PAE) method to suppress the current overshoot, in which the visible light irradiation is introduced into the initial electroforming process, is proposed for the first time. As a result, a reliable memristor with reduced RS fluctuation and enhanced cycling endurance is obtained, and also, the low operating current of 0.06 mA and low powerconsumption of 0.12 mW are achieved, which are about one order of magnitude lower than those of most reported hybrid perovskite‐based memristors. Further experimental evidence indicates that light irradiation plays dual roles: 1) the light‐induced lowering of iodide migration barrier leads to a significant reduction of overshoot current and forming voltage; 2) the enhanced local photoconductivity of the perovskite film shares the overshoot current through the CFs. Both factors limit the total quantity of vacancy defects generated in the electroforming process, thus preventing undesirable overgrowth of the CFs. The present PAE strategy has promise for developing high‐performance memristors.     

Electrode Dependence of Tunneling Electroresistance and Switching Stability in Organic Ferroelectric P(VDF‐TrFE)‐Based Tunnel Junctions

Ferroelectric tunnel junctions (FTJs) are promising candidates for nonvolatile memories and memristor‐based computing circuits. Thus far, most research has focused on FTJs with a perovskite oxide ferroelectric tunnel barrier. As the need for high‐temperature epitaxial film growth challenges the technological application of such inorganic junctions, more easily processable organic ferroelectrics can serve as alternative if large tunneling electroresistance (TER) and good switching durability would persist. This study reports on the performance of FTJs with a spin‐coated ferroelectric P(VDF‐TrFE) copolymer tunnel barrier. The use of three different bottom electrodes, indium tin oxide (ITO), La_0.67Sr_0.33MnO₃, (LSMO), and Nb‐doped SrTiO₃ (STO) are compared and it is shown that the polarity and magnitude of the TER effect depend on their conductivity. The largest TER of up to 10⁷% at room temperature is measured on FTJs with a semiconducting Nb‐doped STO electrode. This large switching effect is attributed to the formation of an extra barrier over the space charge region in the substrate. The organic FTJs exhibit good resistance retention and switching endurance up to 380 K, which is just below the ferroelectric Curie temperature of the P(VDF‐TrFE) barrier.     

Tunable Injection Barrier in Organic Resistive Switches Based on Phase‐Separated Ferroelectric–Semiconductor Blends

Organic non‐volatile resistive bistable diodes based on phase‐separated blends of ferroelectric and semiconducting polymers are fabricated. The polarization field of the ferroelectric modulates the injection barrier at the semiconductor–electrode contact and, hence, the resistance of the comprising diodes. Comparison between the on‐ and off‐current of the switching diodes, with the current measured for semiconductor‐only diodes reveals that the switching occurs between bulk‐limited, i.e., space‐charge‐limited, and injection‐limited current transport. By deliberately varying the HOMO energy of the semiconductor and the work‐function of the metal electrode, it is demonstrated that injection barriers up to 1.6 eV can be surmounted by the ferroelectric polarization yielding on/off current modulations of more than five orders of magnitude. The exponential dependence of the current modulation with a slope of 0.25 eV/decade is rationalized by the magnitude of the injection barrier.     

Artificial Synapses Based on Multiterminal Memtransistors for Neuromorphic Application

Neuromorphic computing, which emulates the biological neural systems could overcome the high‐power consumption issue of conventional von‐Neumann computing. State‐of‐the‐art artificial synapses made of two‐terminal memristors, however, show variability in filament formation and limited capacity due to their inherent single presynaptic input design. Here, a memtransistor‐based arti?cial synapse is realized by integrating a memristor and selector transistor into a multiterminal device using monolayer polycrys‐talline‐MoS₂ grown by a scalable chemical vapor deposition (CVD) process. Notably, the memtransistor offers both drain‐ and gate‐tunable nonvolatile memory functions, which efficiently emulates the long‐term potentiation/depression, spike‐amplitude, and spike‐timing‐dependent plasticity of biological synapses. Moreover, the gate tunability function that is not achievable in two‐terminal memristors, enables significant bipolar resistive states switching up to four orders‐of‐magnitude and high cycling endurance. First‐principles calculations reveal a new resistive switching mechanism driven by the diffusion of double sulfur vacancy perpendicular to the MoS₂ grain boundary, leading to a conducting switching path without the need for a filament forming process. The seamless integration of multiterminal memtransistors may offer another degree‐of‐freedom to tune the synaptic plasticity by a third gate terminal for enabling complex neuromorphic learning.     

Graphene Oxide Quantum Dots Based Memristors with Progressive Conduction Tuning for Artificial Synaptic Learning

Memristors as electronic artificial synapses have attracted increasing attention in neuromorphic computing. Emulation of both “learning” and “forgetting” processes requires a bidirectional progressive adjustment of memristor conductance, which is a challenge for cutting‐edge artificial intelligence. In this work, a memristor device with a structure of Ag/Zr_0.5Hf_0.5O₂:graphene oxide quantum dots/Ag is presented with the feature of bidirectional progressive conductance tuning. The conductance of proposed memristor is adjusted through voltage pulse number, amplitude, and width. A series of voltage pulses with an amplitude of 0.6 V and a width of 30 ns is enough to modulate conductance. The impacts of pulses with different parameters on conductance modulation are investigated, and the potential relationship between pulse amplitude and energy is revealed. Furthermore, it is proved that the pulse with low energy can realize the almost linear conductance regulation, which is beneficial to improve the accuracy of pattern recognition. The bidirectional progressive conduction modulation mimics various plastic synapses, such as spike‐timing‐dependent plasticity and paired‐pulse facilitation. This progressive conduction tuning mechanism might be attributed to the coexistence of tunneling effect and extrinsic electrochemical metallization effect. This work provides one way for memristor to attain attractive features such as bidirectional tuning, low‐power consumption, and fast speed switching that is in urgent demand for further evolution of neuromorphic chips.