Stabilizing amplifier with a programmable load line for characterization of nanodevices with negative differential resistance.

Resistive switching devices and other components with negative differential resistance (NDR) are emerging as possible electronic constituents of next-generation computing architectures. Due to the exhibited NDR effects, switching operations are strongly affected by the presence of resistance in series with the memory cell. Experimental measurements useful in the development of these devices use a deliberate addition of series resistance, which can be done either by integrating resistors on-chip or by connecting external components to the wafer probing system. The former approach is considered inflexible because the resistance value attached to a given device cannot be changed or removed, while the latter approach tends to create parasitic effects that impact controllability and interfere with measurements. In this work, we introduce a circuit design for flexible characterization of two-terminal nanodevices that provides a programmatically adjustable external series resistance while maintaining low parasitic capacitance. Experimental demonstrations show the impact of the series resistance on NDR and resistive switching measurements.

Memristively programmable transistors.

When designing the gate-dielectric of a floating-gate-transistor, one must make a tradeoff between the necessity of providing an ultra-small leakage current behavior for long state retention, and a moderate to high tunneling-rate for fast programming speed. Here we report on a memristively programmable transistor that overcomes this tradeoff. The operation principle is comparable to floating-gate-transistors, but the advantage of the analyzed concept is that ions instead of electrons are used for programming. Since the mass of ions is significantly larger than the effective mass of electrons, gate-dielectrics with higher leakage current levels can be used. We demonstrate the practical feasibility of the device using a proof-of-concept study based on a micrometer-sized thin-film transistor and LT-Spice simulations of 32 nm transistors. Memristively programmable transistors have the potential of high programming endurance and retention times, fast programming speeds, and high scalability.

Current-limiting amplifier for high speed measurement of resistive switching data.

Resistive switching devices, important for emerging memory and neuromorphic applications, face significant challenges related to the control of delicate filamentary states in the oxide material. As a device switches, its rapid conductivity change is involved in a positive feedback process that would lead to runaway destruction of the cell without current, voltage, or energy limitation. Typically, cells are directly patterned on MOS transistors to limit the current, but this approach is very restrictive as the necessary integration limits the materials available as well as the fabrication cycle time. In this article, we propose an external circuit to cycle resistive memory cells, capturing the full transfer curves while driving the cells in a way that suppresses runaway transitions. Using this circuit, we demonstrate the acquisition of 105 I, V loops per second without using on-wafer current limiting transistors. This setup brings voltage sweeping measurements to a relevant timescale for applications and enables many new experimental possibilities for device evaluation in a statistical context.

Design of defect-chemical properties and device performance in memristive systems.

Future development of the modern nanoelectronics and its flagships internet of things, artificial intelligence, and neuromorphic computing is largely associated with memristive elements, offering a spectrum of inevitable functionalities, atomic level scalability, and low-power operation. However, their development is limited by significant variability and still phenomenologically orientated materials' design strategy. Here, we highlight the vital importance of materials' purity, demonstrating that even parts-per-million foreign elements substantially change performance. Appropriate choice of chemistry and amount of doping element selectively enhances the desired functionality. Dopant/impurity-dependent structure and charge/potential distribution in the space-charge layers and cell capacitance determine the device kinetics and functions. The relation between chemical composition/purity and switching/neuromorphic performance is experimentally evidenced, providing directions for a rational design of future memristive devices.

Stateful Three-Input Logic with Memristive Switches.

Memristive switches are able to act as both storage and computing elements, which make them an excellent candidate for beyond-CMOS computing. In this paper, multi-input memristive switch logic is proposed, which enables the function X OR (Y NOR Z) to be performed in a single-step with three memristive switches. This ORNOR logic gate increases the capabilities of memristive switches, improving the overall system efficiency of a memristive switch-based computing architecture. Additionally, a computing system architecture and clocking scheme are proposed to further utilize memristive switching for computation. The system architecture is based on a design where multiple computational function blocks are interconnected and controlled by a master clock that synchronizes system data processing and transfer. The clocking steps to perform a full adder with the ORNOR gate are presented along with simulation results using a physics-based model. The full adder function block is integrated into the system architecture to realize a 64-bit full adder, which is also demonstrated through simulation.

Resistive switching in optoelectronic III-V materials based on deep traps.

Resistive switching random access memories (ReRAM) are promising candidates for energy efficient, fast, and non-volatile universal memories that unite the advantages of RAM and hard drives. Unfortunately, the current ReRAM materials are incompatible with optical interconnects and wires. Optical signal transmission is, however, inevitable for next generation memories in order to overcome the capacity-bandwidth trade-off. Thus, we present here a proof-of-concept of a new type of resistive switching realized in III-V semiconductors, which meet all requirements for the implementation of optoelectronic circuits. This resistive switching effect is based on controlling the spatial positions of vacancy-induced deep traps by stimulated migration, opening and closing a conduction channel through a semi-insulating compensated surface layer. The mechanism is widely applicable to opto-electronically usable III-V compound semiconductors.

Electrically controlled transformation of memristive titanates into mesoporous titanium oxides via incongruent sublimation.

Perovskites such as SrTiO3, BaTiO3, and CaTiO3 have become key materials for future energy-efficient memristive data storage and logic applications due to their ability to switch their resistance reversibly upon application of an external voltage. This resistance switching effect is based on the evolution of nanoscale conducting filaments with different stoichiometry and structure than the original oxide. In order to design and optimize memristive devices, a fundamental understanding of the interaction between electrochemical stress, stoichiometry changes and phase transformations is needed. Here, we follow the approach of investigating these effects in a macroscopic model system. We show that by applying a DC voltage under reducing conditions on a perovskite slab it is possible to induce stoichiometry polarization allowing for a controlled decomposition related to incongruent sublimation of the alkaline earth metal starting in the surface region. This way, self-formed mesoporous layers can be generated which are fully depleted by Sr (or Ba, Ca) but consist of titanium oxides including TiO and Ti3O with tens of micrometre thickness. This illustrates that phase transformations can be induced easily by electrochemical driving forces.

Degradation Kinetics during Oxygen Electrocatalysis on Perovskite-Based Surfaces in Alkaline Media.

The oxygen evolution reaction (OER) during alkaline water electrolysis is the bottleneck of water splitting. Perovskite materials have been particularly proposed as good and economically reasonable electrocatalysts for the OER, showing promise and advantages with respect to classic metallic electrodes. However, the degradation of perovskites during catalysis limits their service lifetime. Recently, the material BaCo0.98Ti0.02O3-δ:Co3O4 was shown to be electrocatalytically and chemically stable during water electrolysis even under industrially relevant conditions. The lifetime of this perovskite-based system is prolonged by a factor of 10 in comparison to that of Pr0.2Ba0.8CoO3-δ and is comparable to that of industrially applied electrodes. Here we report on the degradation kinetics of several OER catalysts at room temperature, comparatively studied by monitoring the oxygen evolution at microelectrodes. A decrease in the reaction rate within a maximum of 60 s is observed, which is related to chemical and/or structural changes at the oxide surface.

A SIMS study of cation and anion diffusion in tantalum oxide.

Ion transport in ceramics of the low-temperature phase of tantalum pentoxide, L-Ta2O5, was examined by means of diffusion experiments and subsequent analysis of diffusion profiles with time-of-flight secondary ion mass spectrometry (ToF-SIMS). 18O/16O isotope anneals were used to investigate oxygen diffusion, and oxygen tracer diffusion coefficients were obtained for the temperature range of 623 ≤ T/K ≤ 873 at an oxygen partial pressure of pO2 = 0.2 bar and for the oxygen partial pressure range of 10-2 ≤ pO2/bar ≤ 100 at a temperature of T = 723 K. Cation diffusion in Ta2O5 was probed by using chemically similar niobium as the diffusant (in the absence of stable tantalum isotopes). Thin films of Nb2O5 were deposited onto Ta2O5 ceramics; diffusion anneals yielded niobium diffusion coefficients for the temperature range of 1073 ≤ T/K ≤ 1223 at an oxygen partial pressure of pO2 = 0.2 bar. Comparison of the measured diffusion coefficients strongly suggests that oxygen is many orders of magnitude more mobile than niobium in L-Ta2O5 at these temperatures and at pO2 = 0.2 bar. The electrical conductivity was also determined in the range 950 ≤ T/K ≤ 1200 and 10-23 ≤ pO2/bar ≤ 10-2. Considered together with the measured diffusion coefficients, the conductivity data indicate that under oxidising conditions conduction is due to oxygen ions above T = 1090-1130 K and due to electron holes below this temperature range. Point-defect models are presented that are consistent with these transport data and with conductivity data in the literature. They suggest that under oxidising conditions oxygen interstitials are the majority ionic charge carriers in L-Ta2O5. The implications for resistive switching devices are discussed.

Interface-driven formation of a two-dimensional dodecagonal fullerene quasicrystal.

Since their discovery, quasicrystals have attracted continuous research interest due to their unique structural and physical properties. Recently, it was demonstrated that dodecagonal quasicrystals could be used as bandgap materials in next-generation photonic devices. However, a full understanding of the formation mechanism of quasicrystals is necessary to control their physical properties. Here we report the formation of a two-dimensional dodecagonal fullerene quasicrystal on a Pt3Ti(111) surface, which can be described in terms of a square-triangle tiling. Employing density functional theory calculations, we identify the complex adsorption energy landscape of the Pt-terminated Pt3Ti surface that is responsible for the quasicrystal formation. We demonstrate the presence of quasicrystal-specific phason strain, which provides the degree of freedom required to accommodate the quasicrystalline structure on the periodic substrate. Our results reveal detailed insight into an interface-driven formation mechanism and open the way to the creation of tailored fullerene quasicrystals with specific physical properties.

SET kinetics of electrochemical metallization cells: influence of counter-electrodes in SiO2/Ag based systems.

The counter-electrode material in resistively switching electrochemical metallization cells (ECMs) is a crucial factor influencing the nucleation of conductive filaments, the equilibrium electrode potentials, and kinetics in the devices, and hence the overall switching characteristics. Here, we demonstrate the influence of the counter-electrode (CE) material on the SET events and the importance of appropriate choice and combination of materials. The counter-electrode material influences the counter-electrode processes at the CE/insulator interface and consequently determines the metal ion concentration in the cells. We measured the switching kinetics for SiO2/Ag based ECM cells using different counter-electrode materials with different electrocatalytic activities towards water reduction, namely platinum, ruthenium, and iridium oxide, as well as titanium nitride and tantalum. The experimental results are fitted using a physical simulation model and are analysed for the limiting factors for fast SET kinetics.

Thermodynamic Ground States of Complex Oxide Heterointerfaces.

The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature equilibrium conductivity measurements. We unambiguously identify two distinct classes of oxide heterostructures: For epitaxial perovskite/perovskite heterointerfaces (LaAlO3/SrTiO3, NdGaO3/SrTiO3, and (La,Sr)(Al,Ta)O3/SrTiO3), we find the 2DEG formation being based on charge transfer into the interface, stabilized by the electric field in the space charge region. In contrast, for amorphous LaAlO3/SrTiO3 and epitaxial γ-Al2O3/SrTiO3 heterostructures, the 2DEG formation mainly relies on the formation and accumulation of oxygen vacancies. This class of 2DEG structures exhibits an unstable interface reconstruction associated with a quenched nonequilibrium state.

Homogeneity and variation of donor doping in Verneuil-grown SrTiO3:Nb single crystals.

The homogeneity of Verneuil-grown SrTiO3:Nb crystals was investigated. Due to the fast crystal growth process, inhomogeneities in the donor dopant distribution and variation in the dislocation density are expected to occur. In fact, for some crystals optical studies show variations in the density of Ti(3+) states on the microscale and a cluster-like surface conductivity was reported in tip-induced resistive switching studies. However, our investigations by TEM, EDX mapping, and 3D atom probe reveal that the Nb donors are distributed in a statistically random manner, indicating that there is clearly no inhomogeneity on the macro-, micro-, and nanoscale in high quality Verneuil-grown crystals. In consequence, the electronic transport in the bulk of donor-doped crystals is homogeneous and it is not significantly channelled by extended defects such as dislocations which justifies using this material, for example, as electronically conducting substrate for epitaxial oxide film growth.

Verification of redox-processes as switching and retention failure mechanisms in Nb:SrTiO3/metal devices.

Nanoscale redox reactions in transition metal oxides are believed to be the physical foundation of memristive devices, which present a highly scalable, low-power alternative for future non-volatile memory devices. The interface between noble metal top electrodes and Nb-doped SrTiO3 single crystals may serve as a prominent but not yet well-understood example of such memristive devices. In this report, we will present experimental evidence that nanoscale redox reactions and the associated valence change mechanism are indeed responsible for the resistance change in noble metal/Nb-doped SrTiO3 junctions with dimensions ranging from the micrometer scale down to the nanometer regime. Direct verification of the valence change mechanism is given by spectromicroscopic characterization of switching filaments. Furthermore, it is found that the resistance change over time is driven by the reoxidation of a previously oxygen-deficient region. The retention times of the low resistance states, accordingly, can be dramatically improved under vacuum conditions as well as through the insertion of a thin Al2O3 layer which prevents this reoxidation. These insights finally confirm the resistive switching mechanism at these interfaces and are therefore of significant importance for the study and application of memristive devices based on Nb-doped SrTiO3 as well as systems with similar switching mechanisms.

Tuning the surface electronic structure of a Pt3Ti(111) electro catalyst.

Increasing the efficiency and stability of bimetallic electro catalysts is particularly important for future clean energy technologies. However, the relationship between the surface termination of these alloys and their catalytic activity is poorly understood. Therefore, we report on fundamental UHV-SPM, LEED, and DFT calculations of the Pt3Ti(111) single crystal surface. Using voltage dependent imaging the surface termination of Pt3Ti(111) was studied with atomic resolution. Combining these images with simulated STM maps based on ab initio DFT calculations allowed us to identify the three upper layers of the Pt3Ti(111) single crystal and their influence upon the surface electronic structure. Our results show that small changes in the composition of the second and third atomic layer are of significant influence upon the surface electronic structure of the Pt3Ti electro catalyst. Furthermore, we provide relevant insights into the dependence of the surface termination on the preparation conditions.

Compact modeling of CRS devices based on ECM cells for memory, logic and neuromorphic applications.

Dynamic physics-based models of resistive switching devices are of great interest for the realization of complex circuits required for memory, logic and neuromorphic applications. Here, we apply such a model of an electrochemical metallization (ECM) cell to complementary resistive switches (CRSs), which are favorable devices to realize ultra-dense passive crossbar arrays. Since a CRS consists of two resistive switching devices, it is straightforward to apply the dynamic ECM model for CRS simulation with MATLAB and SPICE, enabling study of the device behavior in terms of sweep rate and series resistance variations. Furthermore, typical memory access operations as well as basic implication logic operations can be analyzed, revealing requirements for proper spike and level read operations. This basic understanding facilitates applications of massively parallel computing paradigms required for neuromorphic applications.

Nanobatteries in redox-based resistive switches require extension of memristor theory.

Redox-based nanoionic resistive memory cells are one of the most promising emerging nanodevices for future information technology with applications for memory, logic and neuromorphic computing. Recently, the serendipitous discovery of the link between redox-based nanoionic-resistive memory cells and memristors and memristive devices has further intensified the research in this field. Here we show on both a theoretical and an experimental level that nanoionic-type memristive elements are inherently controlled by non-equilibrium states resulting in a nanobattery. As a result, the memristor theory must be extended to fit the observed non-zero-crossing I-V characteristics. The initial electromotive force of the nanobattery depends on the chemistry and the transport properties of the materials system but can also be introduced during redox-based nanoionic-resistive memory cell operations. The emf has a strong impact on the dynamic behaviour of nanoscale memories, and thus, its control is one of the key factors for future device development and accurate modelling.

A tanscriptomics study to elucidate the toxicological mechanism of methylmercury chloride in a human stem cell based in vitro test.

Traditional approaches in evaluating the hazard of drug candidates on the developing offspring are often time-consuming and cost-intensive. Moreover, variations in the toxicological response of different animal species to the tested substance cause severe problems when extrapolating safety dosages for humans. Therefore, more predictive and relevant toxicological systems based on human cell models are required. In the presented study the environmental toxicant methylmercury chloride (MeHgCl), known to cause structural developmental abnormalities in the brain, was used as reference compound to develop a concept contributing to a mechanistic understanding of the toxicity of an investigated substance. Despite the fact, that there are significant data available from animal studies and from poisonings in Japan and Iraq, uncertainties on the mechanism of MeHgCl during human development are still remaining and qualify the substance for further analysis. Transcriptomics analysis in combination with a human cell based in vitro model has been used in order to elucidate the toxicity of MeHgCl at molecular level. Differentiating neural precursor cells that have been exposed continuously to non- and low-cytotoxic concentrations of MeHgCl were investigated. Quantitative change in the mRNA expression profiles of selected genes demonstrated the sensitivity of the cell model and its qualification for a transcriptomics study screening changes in the expression profile of the complete human genome of MeHgCl-treated human neural cells. Potential biomarkers were identified and these candidate marker genes as well as their involvement in a possible toxic mechanism of MeHgCl during the human neurulation process are hereby introduced. The study confirmed the hypothesis that a cellular model based on a human stem cell line can be applied for elucidating unknown mode of actions of developmental toxicants.

Beyond von Neumann--logic operations in passive crossbar arrays alongside memory operations.

The realization of logic operations within passive crossbar memory arrays is a promising approach to expand the fields of application of such architectures. Material implication was recently suggested as the basic function of memristive crossbar junctions, and single bipolar resistive switches (BRS) as well as complementary resistive switches (CRS) were shown to be capable of realizing this logical functionality. Based on a systematic analysis of the Boolean functions, we demonstrate here that 14 of 16 Boolean functions can be realized with a single BRS or CRS cell in at most three sequential cycles. Since the read-out step is independent of the logic operation steps, the result of the logic operation is directly stored to memory, making logic-in-memory applications feasible.

Quantum conductance and switching kinetics of AgI-based microcrossbar cells.

Microcrossbar structured electrochemical metallization (ECM) cells based on silver iodide (AgI) solid electrolyte were fabricated and analyzed in terms of the resistive switching effect. The switching behavior implies the existence of quantized conductance higher than 78 µS which can be identified as a multiple of the single atomic point contact conductivity. The nonlinearity of the switching kinetics has been analyzed in detail. Fast switching in at least 50 ns was observed for short pulse measurements.