Christoph Baeumer

Tunable Carrier Type and Density in Graphene/PbZr0.2Ti0.8O3 Hybrid Structures through Ferroelectric Switching

Bidirectional interdependency between graphene doping level and ferroelectric polarization is demonstrated in graphene/PbZr0.2Ti0.8O3 hybrid structures. The polarization of the PbZr0.2Ti0.8O3 can be effectively switched with graphene electrodes and can in turn alter carrier type and density in the graphene. A complete reversal of the current-voltage hysteresis direction is observed in the graphene when external environmental factors are minimized, converting p-type graphene into n-type with an estimated carrier density change as large as ~10(13) cm(-2). Nonvolatility and reversibility are also demonstrated.

Ferroelectrically driven spatial carrier density modulation in graphene

The next technological leap forward will be enabled by new materials and inventive means of manipulating them. Among the array of candidate materials, graphene has garnered much attention; however, due to the absence of a semiconducting gap, the realization of graphene-based devices often requires complex processing and design. Spatially controlled local potentials, for example, achieved through lithographically defined split-gate configurations, present a possible route to take advantage of this exciting two-dimensional material. Here we demonstrate carrier density modulation in graphene through coupling to an adjacent ferroelectric polarization to create spatially defined potential steps at 180°-domain walls rather than fabrication of local gate electrodes. Periodic arrays of p-i junctions are demonstrated in air (gate tunable to p-n junctions) and density functional theory reveals that the origin of the potential steps is a complex interplay between polarization, chemistry, and defect structures in the graphene/ferroelectric couple.

Spectromicroscopic insights for rational design of redox-based memristive devices.

The demand for highly scalable, low-power devices for data storage and logic operations is strongly stimulating research into resistive switching as a novel concept for future non-volatile memory devices. To meet technological requirements, it is imperative to have a set of material design rules based on fundamental material physics, but deriving such rules is proving challenging. Here, we elucidate both switching mechanism and failure mechanism in the valence-change model material SrTiO3, and on this basis we derive a design rule for failure-resistant devices. Spectromicroscopy reveals that the resistance change during device operation and failure is indeed caused by nanoscale oxygen migration resulting in localized valence changes between Ti4+ and Ti3+. While fast reoxidation typically results in retention failure in SrTiO3, local phase separation within the switching filament stabilizes the retention. Mimicking this phase separation by intentionally introducing retention-stabilization layers with slow oxygen transport improves retention times considerably.

Quantifying redox-induced Schottky barrier variations in memristive devices via in operando spectromicroscopy with graphene electrodes

The continuing revolutionary success of mobile computing and smart devices calls for the development of novel, cost- and energy-efficient memories. Resistive switching is attractive because of, inter alia, increased switching speed and device density. On electrical stimulus, complex nanoscale redox processes are suspected to induce a resistance change in memristive devices. Quantitative information about these processes, which has been experimentally inaccessible so far, is essential for further advances. Here we use in operando spectromicroscopy to verify that redox reactions drive the resistance change. A remarkable agreement between experimental quantification of the redox state and device simulation reveals that changes in donor concentration by a factor of 2–3 at electrode-oxide interfaces cause a modulation of the effective Schottky barrier and lead to >2 orders of magnitude change in device resistance. These findings allow realistic device simulations, opening a route to less empirical and more predictive design of future memory cells.

Anomalous Resistance Hysteresis in Oxide ReRAM: Oxygen Evolution and Reincorporation Revealed by In Situ TEM

The control and rational design of redox-based memristive devices, which are highly attractive candidates for next-generation nonvolatile memory and logic applications, is complicated by competing and poorly understood switching mechanisms, which can result in two coexisting resistance hystereses that have opposite voltage polarity. These competing processes can be defined as regular and anomalous resistive switching. Despite significant characterization efforts, the complex nanoscale redox processes that drive anomalous resistive switching and their implications for current transport remain poorly understood. Here, lateral and vertical mapping of O vacancy concentrations is used during the operation of such devices in situ in an aberration corrected transmission electron microscope to explain the anomalous switching mechanism. It is found that an increase (decrease) in the overall O vacancy concentration within the device after positive (negative) biasing of the Schottky-type electrode is associated with the electrocatalytic release and reincorporation of oxygen at the electrode/oxide interface and is responsible for the resistance change. This fundamental insight presents a novel perspective on resistive switching processes and opens up new technological opportunities for the implementation of memristive devices, as anomalous switching can now be suppressed selectively or used deliberately to achieve the desirable so-called deep Reset.

Surface Termination Conversion during SrTiO3 Thin Film Growth Revealed by X-ray Photoelectron Spectroscopy.

Emerging electrical and magnetic properties of oxide interfaces are often dominated by the termination and stoichiometry of substrates and thin films, which depend critically on the growth conditions. Currently, these quantities have to be measured separately with different sophisticated techniques. This report will demonstrate that the analysis of angle dependent X-ray photoelectron intensity ratios provides a unique tool to determine both termination and stoichiometry simultaneously in a straightforward experiment. Fitting the experimental angle dependence with a simple analytical model directly yields both values. The model is calibrated through the determination of the termination of SrTiO3 single crystals after systematic pulsed laser deposition of sub-monolayer thin films of SrO. We then use the model to demonstrate that during homoepitaxial SrTiO3 growth, excess Sr cations are consumed in a self-organized surface termination conversion before cation defects are incorporated into the film. We show that this termination conversion results in insulating properties of interfaces between polar perovskites and SrTiO3 thin films. These insights about oxide thin film growth can be utilized for interface engineering of oxide heterostructures. In particular, they suggest a recipe for obtaining two-dimensional electron gases at thin film interfaces: SrTiO3 should be deposited slightly Ti-rich to conserve the TiO2-termination.

Subfilamentary Networks Cause Cycle-to-Cycle Variability in Memristive Devices

A major obstacle for the implementation of redox-based memristive memory or logic technology is the large cycle-to-cycle and device-to-device variability. Here, we use spectromicroscopic photoemission threshold analysis and operando XAS analysis to experimentally investigate the microscopic origin of the variability. We find that some devices exhibit variations in the shape of the conductive filament or in the oxygen vacancy distribution at and around the filament. In other cases, even the location of the active filament changes from one cycle to the next. We propose that both effects originate from the coexistence of multiple (sub)filaments and that the active, current-carrying filament may change from cycle to cycle. These findings account for the observed variability in device performance and represent the scientific basis, rather than prior purely empirical engineering approaches, for developing stable memristive devices.

Oxygen Exchange Processes between Oxide Memristive Devices and Water Molecules

Resistive switching based on transition metal oxide memristive devices is suspected to be caused by the electric-field-driven motion and internal redistribution of oxygen vacancies. Deriving the detailed mechanistic picture of the switching process is complicated, however, by the frequently observed influence of the surrounding atmosphere. Specifically, the presence or absence of water vapor in the atmosphere has a strong impact on the switching properties, but the redox reactions between water and the active layer have yet to be clarified. To investigate the role of oxygen and water species during resistive switching in greater detail, isotope labeling experiments in a N2 /H218 O tracer gas atmosphere combined with time-of-flight secondary-ion mass spectrometry are used. It is explicitly demonstrated that during the RESET operation in resistive switching SrTiO3 -based memristive devices, oxygen is incorporated directly from water molecules or oxygen molecules into the active layer. In humid atmospheres, the reaction pathway via water molecules predominates. These findings clearly resolve the role of humidity as both oxidizing agent and source of protonic defects during the RESET operation.

Reduction of the forming voltage through tailored oxygen non-stoichiometry in tantalum oxide ReRAM devices

In this study, we investigated the influence of oxygen non-stoichiometry on the resistive switching performance of tantalum oxide based memristive devices. Thin-films of tantalum oxide were deposited with varying sputter power and oxygen partial pressure. The electroforming voltage was found to decrease with increasing power density or decreased oxygen partial pressure, while the endurance remained stable and the resistance window ROFF/RON was found to increase. In-depth XPS analysis connects these observations to a controllable oxygen sub-stoichiometry in the sputter-deposited films. Our analysis shows that the decrease of the forming voltage results from an increase in carrier density in the as-prepared thin-films, which is induced by the presence of oxygen vacancies.

In-Gap States and Band-Like Transport in Memristive Devices

Point defects such as oxygen vacancies cause emergent phenomena such as resistive switching in transition-metal oxides, but their influence on the electron-transport properties is far from being understood. Here, we employ direct mapping of the electronic structure of a memristive device by spectromicroscopy. We find that oxygen vacancies result in in-gap states that we use as input for single-band transport simulations. Because the in-gap states are situated below the Fermi level, they do not contribute to the current directly but impact the shape of the conduction band. Accordingly, we can describe our devices with band-like transport and tunneling across the Schottky barrier at the interface.