Alexander Zintler

Transition metal oxide dielectric layers have emerged as promising candidates for various relevant applications, such as supercapacitors or memory applications. However, the performance and reliability of these devices can critically depend on their microstructure, which can be strongly influenced by thermal processing and substrate-induced strain. To gain a more in-depth understanding of the microstructural changes, we conducted in situ transmission electron microscopy (TEM) studies of amorphous HfO₂ dielectric layers grown on highly textured (111) substrates. Our results indicate that the minimum required phase transition temperature is 180 °C and that the developed crystallinity is affected by texture transfer. Using in situ TEM and 4D-STEM can provide valuable insights into the fundamental mechanisms underlying the microstructural evolution of dielectric layers and could pave the way for the development of more reliable and efficient devices for future applications.

Advanced nanomaterials are at the core of innovation for the microelectronics industry. Designing, characterizing, and testing two-terminal devices, such as metal-insulator-metal structures, is key to improving material stack design and integration. Electrical biasing within in situ transmission electron microscopy using MEMS-based platforms is a promising technique for nano-characterization under operando conditions. However, conventional focused ion beam sample preparation can introduce parasitic current paths, limiting device performance and leading to overestimated electrical responses. Here we demonstrate connectivity of TEM lamella devices obtained from a novel electrical contacting method based solely on van der Waals forces. This method reduces parasitic leakage currents by at least five orders of magnitude relative to reported preparation approaches. Our methodology enables operation of stack devices inside a microscope with device currents as low as 10 pA. We apply this approach to observe in situ biasing-induced defect formation, providing valuable insights into the behavior of an SrTiO₃-based memristor.

Printed electronics including large‐area sensing, wearables, and bioelectronic systems are often limited to simple circuits and hence it remains a major challenge to efficiently store data and perform computational tasks. Memristors can be considered as ideal candidates for both purposes. Herein, an inkjet‐printed memristor is demonstrated, which can serve as a digital information storage device, or as an artificial synapse for neuromorphic circuits. This is achieved by suitable manipulation of the ion species in the active layer of the device. For digital‐type memristor operation resistive switching is dominated by cation movement after an initial electroforming step. It allows the device to be utilized as non‐volatile digital memristor, which offers high endurance over 12 672 switching cycles and high uniformity at low operating voltages. To use the device as an electroforming‐free, interface‐based, analog‐type memristor, anion migration is exploited which leads to volatile resistive switching. An important figure of merits such as short‐term plasticity with close to biological synapse timescales is demonstrated, for facilitation (10–177 ms), augmentation (10s), and potentiation (35 s). Furthermore, the device is thoroughly studied regarding its metaplasticity for memory formation. Last but not least, the inkjet‐printed artificial synapse shows non‐linear signal integration and low‐frequency filtering capabilities, which renders it a good candidate for neuromorphic computing architectures, such as reservoir computing.

HfO₂-based resistive random-access memory devices are promising candidates for new memory and computing applications. Hereby, scaling of the devices is a key issue, where overall fundamental switching and conduction mechanisms can be easily influenced by changes in the oxide layer thickness. This work addresses the oxide thickness-dependent resistive switching characteristics in Cu/HfO₂/Pt memory devices through bipolar DC switching characterization. Forming, reset, and set characteristics are investigated depending on the oxide layer thickness, revealing a significant difference for thicker compared to thinner films. Thicker samples tend to show a more abrupt reset behavior and a larger set voltage variance, while for thinner samples, a more gradual reset behavior and a low set variance is found. These phenomena can be explained by a model based on thermally assisted electrochemical metallization. Furthermore, to understand the conduction mechanism of the devices, current–voltage curves of the set process were investigated. The devices are found to have an Ohmic conduction mechanism in the lower voltage region generally, while thinner samples tend to show an additional space-charge-limited current conduction mechanism in a higher voltage region.

Resistive random‐access memories are promising candidates for novel computer architectures such as in‐memory computing, multilevel data storage, and neuromorphics. Their working principle is based on electrically stimulated materials changes that allow access to two (digital), multiple (multilevel), or quasi‐continuous (analog) resistive states. However, the stochastic nature of forming and switching the conductive pathway involves complex atomistic defect configurations resulting in considerable variability. This paper reveals that the intricate interplay of 0D and 2D defects can be engineered to achieve reproducible and controlled low‐voltage formation of conducting filaments. The author find that the orientation of grain boundaries in polycrystalline HfO_x is directly related to the required forming voltage of the conducting filaments, unravelling a neglected origin of variability. Based on the realistic atomic structure of grain boundaries obtained from ultra‐high resolution imaging combined with first‐principles calculations including local strain, this paper shows how oxygen vacancy segregation energies and the associated electronic states in the vicinity of the Fermi level govern the formation of conductive pathways in memristive devices. These findings are applicable to non‐amorphous valence change filamentary type memristive device. The results demonstrate that a fundamental atomistic understanding of defect chemistry is pivotal to design memristors as key element of future electronics.

Titanium nitride thin films are used as an electrode material in superconducting (SC) applications and in oxide electronics. By controlling the defect density in the TiN thin film, the electrical properties of the film can achieve low resistivities and a high critical temperature (T_c) close to bulk values. Generally, low defect densities are achieved by stoichiometric growth and a low grain boundary density. Due to the low lattice mismatch of 0.7%, the best performing TiN layers are grown epitaxially on MgO substrates. Here, we report for the first time a T_c of 4.9 K for ultrathin (23 nm), highly textured (111), and stoichiometric TiN films grown on 8.75% lattice mismatch c-cut Al₂O₃ (sapphire) substrates. We demonstrate that with the increasing nitrogen deficiency, the (111) lattice constant increases, which is accompanied by a decrease in T_c. For highly N deficient TiN thin films, no superconductivity could be observed. In addition, a dissociation of grain boundaries (GBs) by the emission of stacking faults could be observed, indicating a combination of two sources for electron scattering defects in the system: (a) volume defects created by nitrogen deficiency and (b) defects created by the presence of GBs. For all samples, the average grain boundary distance is kept constant by a miscut of the c-cut sapphire substrate, which allows us to distinguish the effect of nitrogen deficiency and grain boundary density. These properties and surface roughness govern the electrical performance of the films and influence the compatibility as an electrode material in the respective application. This study aims to provide detailed and scale-bridging insights into the structural and microstructural response to nitrogen deficiency in the c-Al₂O₃/TiN system, as it is a promising candidate for applications in state-of-the-art systems such as oxide electronic thin film stacks or SC applications.

Birth of a grain boundary: In situ TEM Observation of the Microstructure Evolution in HfO2 Based Memristors - Volume 27 Issue S1

This work investigates the transition from digital to gradual or analog resistive switching in yttrium oxide‐based resistive random‐access memory devices. It is shown that this transition is determined by the amount of oxygen in the functional layer. A homogeneous reduction of the oxygen content not only reduces the electroforming voltage, allowing for forming‐free devices, but also decreases the voltage operation window of switching, thereby reducing intra‐device variability. The most important effect as the dielectric becomes substoichiometric by oxygen engineering is that more intermediate (quantized) conduction states are accessible. A key factor for this reproducibly controllable behavior is the reduced local heat dissipation in the filament region due to the increased thermal conductivity of the oxygen depleted layer. The improved accessibility of quantized resistance states results in a semi‐gradual switching both for the set and reset processes, as strongly desired for multi‐bit storage and for an accurate definition of the synaptic weights in neuromorphic systems. A theoretical model based on the physics of mesoscopic structures describing current transport through a nano‐constriction including asymmetric potential drops at the electrodes and non‐linear conductance quantization is provided. The results contribute to a deeper understanding on how to tailor materials properties for novel memristive functionalities.