Mechanical Manipulation of Nano-Twinned Ferroelectric Domain Structures for Multilevel Data Storage

Ferroelectric materials feature a switchable spontaneous electric polarization and can enable low-power logic and nonvolatile memories. These applications require reliable and precise control of ferroelectric domains and domain walls in ferroelectric thin films. Mechanical manipulation is a promising route to engineer ferroelectric domains, but it has proved ineffective when going beyond a critical thickness. Here, multi-step 90° switching polarization reversal processes in (111)-oriented PbZr_0.2Ti_0.8O₃ thin films by applying mechanical forces along the direction parallel to the domain bands are reported. By probing the interrelationships between the relevant order parameters, coupled lattice distortion and piezoelectricity is revealed to facilitate domain switching from downward to upward in PbZr_0.2Ti_0.8O₃, a mechanism that is supported by the evolution of domains and electrical performances at different temperatures and under varying pressures, respectively. The multi-step domain reversal processes render PbZr_0.2Ti_0.8O₃ thin films an excellent candidate for multilevel data storage. The study's results have implications for the manipulation of polarization switching in ferroelectrics and open an avenue to domain reversal driven by mechanical loads for the development of next-generation ferroelectric devices.     

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.     

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.     

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.     

Impact of Dynamic Interlayer Interactions on Thermal Conductivity of Ca3Co4O9

The phonon thermal conductivity of misfit-layered Ca₃Co₄O₉ has been calculated by perturbed molecular dynamics using a classical force field. Detailed numerical analyses reveal that, in spite of its smaller cross-sectional area, the CoO₂ layer transports more heat than the thicker rock salt (RS) layer, although its local thermal conduction is more suppressed than in another layered cobaltite, Na _x CoO₂. The origins of these differences have been elucidated through careful examination of the atomic arrangements in each layer. Since thermal conduction in the RS layer can be reduced without deteriorating electronic properties for which the CoO₂ layer is responsible, it is suggested that the RS layer should be modified to further suppress the overall in-plane thermal conductivity. Computational experiments with increasing number of Ca–O planes in the RS layer showed the opposite trend to what can be predicted based on the misfit between two dissimilar layers. Further analyses to reveal the origin of these unexpected results provide yet another strategy to further decrease the thermal conductivity, namely to control the dynamic interference between atoms across the interface between two layers.     

Improved performance of ITO/TiO2/HfO2/Pt random resistive accessory memory by nitrogen annealing treatment

Resistive switching (RS) characteristics of TiO₂/HfO₂ bilayer memory devices annealed under N₂ and O₂ ambient were investigated in this work. It was found that the improved RS properties were obtained in N₂ annealing atmosphere, which exhibited good endurance of more than 100 times in direct current measurement mode and data retention properties of 10⁴ s at 85 °C. To clarify the effect of annealing treatment on the devices in various atmospheres, conduction mechanism, which is related to the RS properties was analyzed. The results showed that the space charge limited current (SCLC) was the dominant conduction mechanism in HRS for the as prepared device; for the device annealed in N₂, the conduction mechanism was dominated by Pool–Frenkel emission. It can be induced that the conduction mechanism variation in N₂ was attributed to the increase of oxygen vacancies in the switching layer, which was the main reason for the improvement of RS characteristics. Lastly, we switched the operation voltage from the Pt to the ITO electrode of the double layer RRAMs, and found that better endurance and smaller operation voltages were obtained when it was applied on the Pt electrode.     

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.     

Correlated Lattice Instability and Emergent Charged Domain Walls at Oxide Heterointerfaces

Charged domain walls provide possibilities in effectively manipulating electrons at nanoscales for developing next‐generation electronic devices. Here, using the atom‐resolved imaging and spectroscopy on LaAlO₃/SrTiO₃//NdGaO₃ heterostructures, the evolution of correlated lattice instability and charged domain walls is visualized crossing the conducting LaAlO₃/SrTiO₃ heterointerface. When increasing the SrTiO₃ layer thickness to 20 unit cells and above, both LaAlO₃ and SrTiO₃ layers begin to exhibit measurable polar displacements to form a tail‐to‐tail charged domain wall at the LaAlO₃/SrTiO₃ interface, resulting in the charged redistribution within the 2‐nm‐thick SrTiO₃ layer close to the LaAlO₃/SrTiO₃ interface. The mobile charges in different heterostructures can be estimated by summing up Ti³⁺ concentrations in the conducting channel, which is sandwiched by SrTiO₃ layers with interdiffusion and/or oxygen octahedral rotations. Those estimated mobile charges are quantitatively consistent with results from Hall measurements. The results not only shed light on complex oxide heterointerfaces, but also pave a new path to nanoscale charge engineering.     

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.     

Influence of the manufacturing process on the electrical properties of thin (<4 nm) Hafnium based high-k stacks observed with CAFM

In this work, the dependence of the electrical characteristics of some thin (<4 nm) HfO₂, HfSiO and HfO₂/SiO₂ stacks on their manufacturing process is studied at the nanoscale. Topography, current maps and current–voltage (I–V) characteristics have been collected by conductive atomic force microscope (CAFM), which show that their conductivity depends on some manufacturing parameters. Increasing the annealing temperature, physical thickness or Hafnium content makes the structure less conductive.     

Direct Observation of Capacitor Switching Using Planar Electrodes

Ferroelectric polarization switching in epitaxial (110) BiFeO₃ films is studied using piezoresponse force microscopy of a model in‐plane capacitor structure. The electrode orientation is chosen such that only two active domain variants exist. Studies of the kinetics of domain evolution allows clear visualization of nucleation sites, as well as forward and lateral growth stages of domain formation. It is found that the location of the reverse‐domain nucleation is correlated with the direction of switching in a way that the polarization in the domains nucleated at an electrode is always directed away from it. The role of interface charge injection and surface screening charge on switching mechanisms is explored, and the nucleation is shown to be controllable by the bias history of the sample. Finally, the manipulation of domain nucleation through domain structure engineering is illustrated. These studies pave the way for the engineering and design of the ferroelectric device structures through control of individual steps of the switching process.     

Electromechanics of Domain Walls in Uniaxial Ferroelectrics

Piezoresponse 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.     

Comprehensive investigation of trap-assisted conduction in ultra-thin SrTiO3 layers

The conduction in thin SrTiO₃ (STO) films has been investigated. Characterization of leakage current as a function of bias, temperature and film thickness indicates field enhanced hopping as the dominating conduction mechanism. The findings were confirmed by photo-conductivity measurements and agree well with simulation results.     

Forming-Free Reversible Bipolar Resistive Switching Behavior in Al-Doped HfO<Subscript>2</Subscript> Metal–Insulator–Metal Devices

Resistive switching (RS) characteristics are investigated in fabricated Al-doped HfO₂ metal–insulator–metal devices. It is proposed that oxygen vacancies in Al-doped HfO₂ devices play a key role as electron trap centers, leading to the forming-free reversible bipolar resistance switching behavior. The conduction mechanism can be explained by electron trapping and detrapping from such oxygen vacancy-related traps in the Al-doped HfO₂ films and is dominated by a trap-controlled space-charge-limited current (SCLC) mechanism. A large RS ratio (~10⁶) and excellent retention characteristics are also observed at room temperature as well as at 85°C. Such devices have potential for application in nonvolatile random-access memory.     

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.     

Ferroelectric Self‐Poling,Switching, and Monoclinic Domain Configuration in BiFeO3 Thin Films

Self‐poling of ferroelectric films, i.e., a preferred, uniform direction of the ferroelectric polarization in as‐grown samples is often observed yet poorly understood despite its importance for device applications. The multiferroic perovskite BiFeO₃, which crystallizes in two distinct structural polymorphs depending on applied epitaxial strain, is well known to exhibit self‐poling. This study investigates the effect of self‐poling on the monoclinic domain configuration and the switching properties of the two polymorphs of BiFeO₃ (R′ and T′) in thin films grown on LaAlO₃ substrates with slightly different La_0.3Sr_0.7MnO₃ buffer layers. This study shows that the polarization state formed during the growth acts as “imprint” on the polarization and that switching the polarization away from this self‐poled direction can only be done at the expense of the sample's monoclinic domain configuration. The observed reduction of the monoclinic domain size is largely reversible; hence, the domain size is restored when the polarization is switched back to its original orientation. This is a direct consequence of the growth taking place in the polar phase (below T_c). Switching the polarization away from the preferred configuration, in which defects and domain patterns synergistically minimize the system's energy, leads to a domain state with smaller (and more highly strained and distorted) monoclinic domains.     

Gas Sensing of NiO‐SCCNT Core–Shell Heterostructures: Optimization by Radial Modulation of the Hole‐Accumulation Layer

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al₂O₃ dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al₂O₃–SCCNT, Al₂O₃–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region.     

Anodic processes in the chemical and electrochemical etching of Si crystals in acid-fluoride solutions: Pore formation mechanism

The interaction of heavily doped p- and n-type Si crystals with hydrofluoric acid in the dark with and without contact with metals having greatly differing work functions (Ag and Pd) is studied. The dependences of the dissolution rates of Si crystals in HF solutions that contain oxidizing agents with different redox potentials (FeCl₃, V₂O₅ and CrO₃) on the type and level of silicon doping are determined. Analysis of the experimental data suggests that valence-band holes in silicon are not directly involved in the anodic reactions of silicon oxidation and dissolution and their generation in crystals does not limit the rate of these processes. It is also shown that the character and rate of the chemical process leading to silicon dissolution in HF-containing electrolytes are determined by the interfacial potential attained at the semiconductor–electrolyte interface. The mechanism of electrochemical pore formation in silicon crystals is discussed in terms of selfconsistent cooperative reactions of nucleophilic substitution between chemisorbed fluorine anions and coordination- saturated silicon atoms in the crystal subsurface layer. A specific feature of these reactions for silicon crystals is that vacant nonbonding d ² sp ³ orbitals of Si atoms, associated with sixfold degenerate states corresponding to the Δ valley of the conduction band, are involved in the formation of intermediate complexes. According to the suggested model, the pore-formation process spontaneously develops in local regions of the interface under the action of the interfacial potential in the adsorption layer and occurs as a result of the detachment of (SiF₂) _n polymer chains from the crystal. Just this process leads to the preferential propagation of pores along the <100> crystallographic directions. The thermodynamic aspects of pore nucleation and the effect of the potential drop across the interface, conduction type, and free-carrier concentration in the crystal on the pore size and structure are discussed. The concepts developed in the study can consistently account for experimental facts characterizing the etching of silicon crystals with various electrical parameters under various conditions providing the anodic polarization of crystals in HF-containing solutions.     

Conduction mechanisms and an evidence for phonon-assisted conduction process in thin high-k HfxTiySizO films

Electrical behavior of high-k Hf_xTi_ySi_zO layers with different Hf:Ti ratios in the film have been investigated. The films are prepared by MOCVD using novel single-source precursors chemistry. Oxide and interface charges, leakage currents and conduction mechanisms are found to be a strong function of the film composition. The films with lower Hf content show lower level of oxide and interface charges and higher dielectric constant whereas those with higher Hf content have better leakage current properties. It is established that in the films with lower Hf content the conduction is governed by a phonon-assisted process. The change of the conduction mechanism from Poole–Frenkel emission to phonon-assisted tunneling is assigned to possible structural changes which take place when changing the composition of the films.     

Air‐Stable Cesium Lead Iodide Perovskite for Ultra‐Low Operating Voltage Resistive Switching

CsPbX₃ (X = halide, Cl, Br, or I) all‐inorganic halide perovskites (IHPs) are regarded as promising functional materials because of their tunable optoelectronic characteristics and superior stability to organic–inorganic hybrid halide perovskites. Herein, nonvolatile resistive switching (RS) memory devices based on all‐inorganic CsPbI₃ perovskite are reported. An air‐stable CsPbI₃ perovskite film with a thickness of only 200 nm is successfully synthesized on a platinum‐coated silicon substrate using low temperature all‐solution process. The RS memory devices of Ag/polymethylmethacrylate (PMMA)/CsPbI₃/Pt/Ti/SiO₂/Si structure exhibit reproducible and reliable bipolar switching characteristics with an ultralow operating voltage (<+0.2 V), high on/off ratio (>10⁶), reversible RS by pulse voltage operation (pulse duration < 1 ms), and multilevel data storage. The mechanical flexibility of the CsPbI₃ perovskite RS memory device on a flexible substrate is also successfully confirmed. With analyzing the influence of phase transition in CsPbI₃ on RS characteristics, a mechanism involving conducting filaments formed by metal cation migration is proposed to explain the RS behavior of the memory device. This study will contribute to the understanding of the intrinsic characteristics of IHPs for low‐voltage resistive switching and demonstrate the huge potential of them for use in low‐power consumption nonvolatile memory devices on next‐generation computing systems.