Hafnium oxide plays an important role as a dielectric material in various thin-film electronic devices such as transistors and resistive or ferroelectric memory. The crystallographic and electronic structure of the hafnia layer often depends critically on its composition and defect structure. Here, we report two novel defectstabilized polymorphs of substoichiometric HfO 2−x with semiconducting properties that are of particular interest for resistive switching digital or analog memory devices. The thin-film samples are synthesized by molecular beam epitaxy with oxygen engineering that allows us to cover the whole range of metallic Hf with oxygen interstitials to HfO 2 . The crystal and defect structures, in particular of a cubic low-temperature phase c-HfO 1.7 and a hexagonal phase hcp-HfO 0.7 are identified by X-ray diffraction, in vacuo electron spectroscopic, and transmission electron microscopic methods. With the help of UV/Vis transmission data, we propose a consistent band structure model for the whole oxidation range involving oxygen vacancy-induced in-gap defect states. Our comprehensive study of engineered hafnia thin films has an impact on the design of resistive memory devices and can be transferred to chemically similar suboxide systems.

A model device based on an epitaxial stack combination of titanium nitride (111) and monoclinic hafnia (11true1¯) is grown onto a c‐cut Al2O3‐substrate to target the role of grain boundaries in resistive switching. The texture transfer results in 120° in‐plane rotated m‐HfO2 grains, and thus, in a defined subset of allowed grain boundary orientations of high symmetry. These engineered grain boundaries thread the whole dielectric layer, thereby providing predefined breakdown paths for electroforming‐free resistive random access memory devices. Combining X‐ray diffraction and scanning transmission electron microscopy (STEM)–based localized automated crystal orientation mapping (ACOM), a nanoscale picture of crystal growth and grain boundary orientation is obtained. High‐resolution STEM reveals low‐energy grain boundaries with facing (1¯1¯2¯) and (true1¯21) surfaces. The uniform distribution of forming voltages below 2 V—within the operation regime—and the stable switching voltages indicates reduced intra‐ and device‐to‐device variation in grain boundary engineered hafnium‐oxide‐based random access memory devices.

In this work, analysis and simulation of all experimentally observed switching modes in hafnium oxide based resistive random access memories are carried out using a simplified electrical conduction model. To achieve switching mode variation, two metal-insulator-metal cells with identical stack combination, but varying oxygen stoichiometry of the hafnia layer, namely, stoichiometric vs highly deficient, are considered. To access the individual switching modes, the devices were subjected to a variety of cycling conditions comprising different voltage and current ranges. For modeling the device behavior, a single or two antiserially connected memdiodes (diode with memory) were utilized. In this way, successful compact simulation of unipolar, bipolar, threshold, and complementary resistive switching modes is accomplished confirming the coexistence of two switching mechanisms of opposite polarity as the basis for all observable switching phenomena in this material. We show that only calibration of the outer current–voltage loops with the memdiode model is necessary for predicting the device behavior in the defined region revealing additional information on the switching process. The correspondence of each memdiode device with the conduction characteristics of the individual top and bottom metal-oxide contacts allows one to assess the role played by each interface in the switching process separately. This identification paves the path for a future improvement of the device performance and functionality by means of appropriate interface engineering.

Within this article, it is shown that an electrochemical defluorination and additional fluorination of Ruddlesden−Poppertype La 2 NiO 3 F 2 is possible within all-solid-state fluoride-ion batteries. Structural changes within the reduced and oxidized phases have been examined by X-ray diffraction studies at different states of charging and discharging. The synthesis of the oxidized phase La 2 NiO 3 F 2+x proved to be successful by structural analysis using both X-ray powder diffraction and automated electron diffraction tomography techniques. The structural reversibility on re-fluorinating and re-defluorinating is also demonstrated. Moreover, the influence of different sequences of consecutive reduction and oxidation steps on the formed phases has been investigated. The observed structural changes have been compared to changes in phases obtained via other topochemical modification approaches such as hydride-based reduction and oxidative fluorination using F 2 gas, highlighting the potential of such electrochemical reactions as alternative synthesis routes. Furthermore, the electrochemical routes represent safe and controllable synthesis approaches for novel phases, which cannot be synthesized via other topochemical methods. Additionally, side reactions, occurring alongside the desired electrochemical reactions, have been addressed and the cycling performance has been studied.

This work addresses the thermal stability of bipolar resistive switching in yttrium oxide-based resistive random access memory revealed through the temperature dependence of the DC switching behavior. The operation voltages, current levels, and charge transport mechanisms are investigated at 25 °C, 85 °C, and 125 °C, and show overall good temperature immunity. The set and reset voltages, as well as the device resistance in both the high and low resistive states, are found to scale inversely with increasing temperatures. The Schottky-barrier height was observed to increase from approximately 1.02 eV at 25 °C to approximately 1.35 eV at 125 °C, an uncommon behavior explained by interface phenomena.