Texture Transfer in Dielectric Layers via Nanocrystalline Networks: Insights from in Situ 4D-STEM.

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.

Weld-free mounting of lamellae for electrical biasing operando TEM.

Recent advances in microelectromechanical systems (MEMS)-based substrates and sample holders for in situ transmission electron microscopy (TEM) are currently enabling exciting new opportunities for the nanoscale investigation of materials and devices. The ability to perform electrical testing while simultaneously capturing the wide spectrum of signals detectable in a TEM, including structural, chemical, and even electronic contrast, represents a significant milestone in the realm of nanoelectronics. In situ studies hold particular promise for the development of Metal-Insulator-Metal (MIM) devices for use in next-generation computing. However, achieving successful device operation in the TEM typically necessitates meticulous sample preparation involving focused ion beam (FIB) systems. Conducting contamination introduced during the FIB thinning process and subsequent attachment of the sample onto a MEMS-based chip remains a formidable challenge. This article delineates an improved FIB-based sample preparation methodology that results in good electrical connectivity and operational functionality across various MIM devices. To exemplify the efficacy of the sample preparation technique, we demonstrate preparation of a clean cross section extracted from a Au/Pt/BaSrTiO3/SrMoO3 tunable capacitor (varactor). The FIB-prepared TEM lamella mounted on a MEMS-based chip showed current levels in the tens of picoamperes range at 0.1 V. Furthermore, the electric response and current density of the TEM lamella device closely align with macro-scale devices. These samples exhibit comparable current densities to their macro-sized counterparts thus validating the sample preparation process and confirming device connectivity. The simultaneous operation and TEM characterization of electronic devices enabled by this process enables direct correlation between device structure and function, which could prove pivotal in the development of new MIM systems.

Element-Specific Study of Magnetic Anisotropy and Hardening in SmCo5-xCux Thin Films.

This work investigates the effect of copper substitution on the magnetic properties of SmCo5 thin films synthesized by molecular beam epitaxy. A series of thin films with varying concentrations of Cu were grown under otherwise identical conditions to disentangle structural and compositional effects on the magnetic behavior. The combined experimental and theoretical studies show that Cu substitution at the Co3g sites not only stabilizes the formation of the SmCo5 structure but also enhances magnetic anisotropy and coercivity. Density functional theory calculations indicate that Sm(Co4Cu3g)5 possesses a higher single-ion anisotropy as compared to pure SmCo5. In addition, X-ray magnetic circular dichroism reveals that Cu substitution causes an increasing decoupling of the Sm 4f and Co 3d moments. Scanning transmission electron microscopy confirms predominantly SmCo5 phase formation and reveals nanoscale inhomogeneities in the Cu and Co distribution. Our study based on thin film model systems and advanced characterization as well as modeling reveals novel aspects of the complex interplay of intrinsic and extrinsic contributions to magnetic hysteresis in rare-earth-based magnets, i.e., the combination of increased intrinsic anisotropy due to Cu substitution and the extrinsic effect of inhomogeneous elemental distribution of Cu and Co.

Impact of Strain Engineering on Antiferroelectricity in NaNbO3 Thin Films.

Thin films of NaNbO3 were grown on various substrates to investigate the effect of epitaxial strain on their structural and electrical properties. Reciprocal space maps confirmed the presence of epitaxial strain from +0.8% to -1.2%. A bulk-like antipolar ground state was detected via structural characterization for NaNbO3 thin films grown with strains ranging from a compressive strain of 0.8% to small tensile strains, up to -0.2%. For larger tensile strains on the other hand, no indication of antipolar displacements can be detected, even beyond the relaxation of the film at larger thicknesses. Electrical characterization revealed a ferroelectric hysteresis loop for thin films under a strain of +0.8% to -0.2%, while the films under larger tensile strain showed no out-of-plane polarization component. However, the films with a compressive strain of 0.8% present a saturation polarization of up to 55 µC·cm-2, more than twice as large for films grown under conditions with small strain, which is also larger than the highest values reported for bulk materials. Our results indicate the high potential for strain engineering in antiferroelectric materials, as the antipolar ground state could be retained with compressive strain. The observed enhancement of the saturation polarization by strain allows for substantial increase of energy density of the capacitors with antiferroelectric materials.

Recent Advances and Future Prospects for Memristive Materials, Devices, and Systems.

Memristive technology has been rapidly emerging as a potential alternative to traditional CMOS technology, which is facing fundamental limitations in its development. Since oxide-based resistive switches were demonstrated as memristors in 2008, memristive devices have garnered significant attention due to their biomimetic memory properties, which promise to significantly improve power consumption in computing applications. Here, we provide a comprehensive overview of recent advances in memristive technology, including memristive devices, theory, algorithms, architectures, and systems. In addition, we discuss research directions for various applications of memristive technology including hardware accelerators for artificial intelligence, in-sensor computing, and probabilistic computing. Finally, we provide a forward-looking perspective on the future of memristive technology, outlining the challenges and opportunities for further research and innovation in this field. By providing an up-to-date overview of the state-of-the-art in memristive technology, this review aims to inform and inspire further research in this field.

Crystal and Electronic Structure of Oxygen Vacancy Stabilized Rhombohedral Hafnium Oxide.

Hafnium oxide is an outstanding candidate for next-generation nonvolatile memory solutions such as OxRAM (oxide-based resistive memory) and FeRAM (ferroelectric random access memory). A key parameter for OxRAM is the controlled oxygen deficiency in HfO2-x which eventually is associated with structural changes. Here, we expand the view on the recently identified (semi-)conducting low-temperature pseudocubic phase of reduced hafnium oxide by further X-ray diffraction analysis and density functional theory (DFT) simulation and reveal its rhombohedral nature. By performing total energy and electronic structure calculations, we investigate phase stability and band structure modifications in the presence of oxygen vacancies. With increasing oxygen vacancy concentration, the material transforms from the well-known monoclinic structure to a (pseudocubic) polar rhombohedral r-HfO2-x structure. The DFT analysis shows that r-HfO2-x is not merely epitaxy-induced but may exist as a relaxed compound. Furthermore, the electronic structure of r-HfO2-x as determined by X-ray photoelectron spectroscopy and UV/Vis spectroscopy corresponds very well with the DFT-based prediction of a conducting defect band. The existence of a substoichiometric (semi-)conducting phase of HfO2-x is obviously an important ingredient to understand the mechanism of resistive switching in hafnium-oxide-based OxRAM.

Tailoring Optical Properties in Transparent Highly Conducting Perovskites by Cationic Substitution.

SrMoO3 , SrNbO3 , and SrVO3 are remarkable highly conducting d1 (V, Nb) or d2 (Mo) perovskite metals with an intrinsically high transparency in the visible. A key scientific question is how the optical properties of these materials can be manipulated to make them suitable for applications as transparent electrodes and in plasmonics. Here, it is shown how 3d/4d cationic substitution in perovskites tailors the relevant materials parameters, i.e., optical transition energy and plasma frequency. With the example of the solid-state solution SrV1- x Mox O3 , it is shown that the absorption and reflection edges can be shifted to the edges of the visible light spectrum, resulting in a material that has the potential to outperform indium tin oxide (ITO) due to its extremely low sheet resistance. An optimum for x = 0.5, where a resistivity of 32 µΩ cm (≈12 Ω sq-1 ) is paired with a transmittance above 84% in the whole visible spectrum is found. Quantitative comparison between experiments and electronic structure calculations show that the shift of the plasma frequency is governed by the interplay of d-band filling and electronic correlations. This study advances the knowledge about the peculiar class of highly conducting perovskites toward sustainable transparent conductors and emergent plasmonics.

Fast Fitting of the Dynamic Memdiode Model to the Conduction Characteristics of RRAM Devices Using Convolutional Neural Networks.

In this paper, the use of Artificial Neural Networks (ANNs) in the form of Convolutional Neural Networks (AlexNET) for the fast and energy-efficient fitting of the Dynamic Memdiode Model (DMM) to the conduction characteristics of bipolar-type resistive switching (RS) devices is investigated. Despite an initial computationally intensive training phase the ANNs allow obtaining a mapping between the experimental Current-Voltage (I-V) curve and the corresponding DMM parameters without incurring a costly iterative process as typically considered in error minimization-based optimization algorithms. In order to demonstrate the fitting capabilities of the proposed approach, a complete set of I-Vs obtained from Y2O3-based RRAM devices, fabricated with different oxidation conditions and measured with different current compliances, is considered. In this way, in addition to the intrinsic RS variability, extrinsic variation is achieved by means of external factors (oxygen content and damage control during the set process). We show that the reported method provides a significant reduction of the fitting time (one order of magnitude), especially in the case of large data sets. This issue is crucial when the extraction of the model parameters and their statistical characterization are required.

Controlling the Formation of Conductive Pathways in Memristive Devices.

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 HfOx 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.

Structural and Electrical Response of Emerging Memories Exposed to Heavy Ion Radiation.

Hafnium oxide- and GeSbTe-based functional layers are promising candidates in material systems for emerging memory technologies. They are also discussed as contenders for radiation-harsh environment applications. Testing the resilience against ion radiation is of high importance to identify materials that are feasible for future applications of emerging memory technologies like oxide-based, ferroelectric, and phase-change random-access memory. Induced changes of the crystalline and microscopic structure have to be considered as they are directly related to the memory states and failure mechanisms of the emerging memory technologies. Therefore, we present heavy ion irradiation-induced effects in emerging memories based on different memory materials, in particular, HfO2-, HfZrO2-, as well as GeSbTe-based thin films. This study reveals that the initial crystallinity, composition, and microstructure of the memory materials have a fundamental influence on their interaction with Au swift heavy ions. With this, we provide a test protocol for irradiation experiments of hafnium oxide- and GeSbTe-based emerging memories, combining structural investigations by X-ray diffraction on a macroscopic, scanning transmission electron microscopy on a microscopic scale, and electrical characterization of real devices. Such fundamental studies can be also of importance for future applications, considering the transition of digital to analog memories with a multitude of resistance states.

Enhanced Conductivity and Microstructure in Highly Textured TiN1-x /c-Al2O3 Thin Films.

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.

Defect-Stabilized Substoichiometric Polymorphs of Hafnium Oxide with Semiconducting Properties.

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 defect-stabilized polymorphs of substoichiometric HfO2-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 HfO2. The crystal and defect structures, in particular of a cubic low-temperature phase c-HfO1.7 and a hexagonal phase hcp-HfO0.7 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.

Energy Level Alignment at the Cobalt Phosphate/Electrolyte Interface: Intrinsic Stability vs Interfacial Chemical Reactions in 5 V Lithium Ion Batteries.

The intrinsic stability of the 5 V LiCoPO4-LiCo2P3O10 thin-film (carbon-free) cathode material coated with MoO3 thin layer is studied using a comprehensive synchrotron electron spectroscopy in situ approach combined with first-principle calculations. The atomic-molecular level study demonstrates fully reversible electronic properties of the cathode after the first electrochemical cycle. The polyanionic oxide is not involved in chemical reactions with the fluoroethylene-containing liquid electrolyte even when charged to 5.1 V vs Li+/Li. The high stability of the cathode is explained on the basis of the developed energy level model. In contrast, the chemical composition of the cathode-electrolyte interface evolves continuously by involving MoO3 in the decomposition reaction with consequent leaching of oxide from the surface. The proposed mechanisms of chemical reactions are attributed to external electrolyte oxidation via charge transfer from the relevant electron level to the MoO3 valence band state and internal electrolyte oxidation via proton transfer to the solvents. This study provides a deeper insight into the development of both a doping strategy to enhance the electronic conductivity of high-voltage cathode materials and an efficient surface coating against unfavorable interfacial chemical reactions.

Structural and Magnetic Properties of BaFeO2.667 Synthesized by Oxidizing BaFeO2.5 Obtained via Nebulized Spray Pyrolysis.

A vacancy-ordered perovskite-type compound Ba3Fe3O8 (BaFeO2.667) was prepared by oxidizing BaFeO2.5 (P21/c) with the latter compound obtained by a spray pyrolysis technique. The structure of Ba3Fe3O8 was found to be isotypic to Ba3Fe3O7F (P21/m) and can be written as Ba3Fe3+2Fe4+1O8. Mössbauer spectroscopy and ab initio calculations were used to confirm mixed iron oxidation states, showing allocation of the tetravalent iron species on the tetrahedral site, and octahedral as well as square pyramidal coordination for the trivalent species within a G-type antiferromagnetic ordering. The uptake and release of oxygen were investigated over a broad temperature range from room temperature to 1100 °C under pure oxygen and ambient atmosphere via a combination of DTA/TG and variable temperature diffraction measurements. The compound exhibited a strong lattice enthalpy driven reduction to monoclinic and cubic BaFeO2.5 at elevated temperatures.

Epitaxy Induced Highly Ordered Sm2Co17-SmCo5 Nanoscale Thin-Film Magnets.

Utilizing the molecular beam epitaxy technique, a nanoscale thin-film magnet of c-axis-oriented Sm2Co17 and SmCo5 phases is stabilized. While typically in the prototype Sm(Co, Fe, Cu, Zr)7.5-8 pinning-type magnets, an ordered nanocomposite is formed by complex thermal treatments, here, a one-step approach to induce controlled phase separation in a binary Sm-Co system is shown. A detailed analysis of the extended X-ray absorption fine structure confirmed the coexistence of Sm2Co17 and SmCo5 phases with 65% Sm2Co17 and 35% SmCo5. The SmCo5 phase is stabilized directly on an Al2O3 substrate up to a thickness of 4 nm followed by a matrix of Sm2Co17 intermixed with SmCo5. This structural transition takes place through coherent atomic layers, as revealed by scanning transmission electron microscopy. Highly crystalline growth of well-aligned Sm2Co17 and SmCo5 phases with coherent interfaces result in strong exchange interaction, leading to enhanced magnetization and magnetic coupling. The arrangement of Sm2Co17 and SmCo5 phases at the nanoscale is reflected in the observed magnetocrystalline anisotropy and coercivity. As next-generation permanent magnets require designing of materials at an atomic level, this work enhances our understanding of self-assembling and functioning of nanophased magnets and contributes to establishing new concepts to engineer the microstructure for beyond state-of-the-art magnets.

All-Oxide Varactor Electromechanical Properties Extracted by Highly Accurate Modeling Over a Broad Frequency and Electric Bias Range.

Since the dielectric permittivity of ferroelectric materials depends on the electric field, they allow designing switchable and continuously tunable devices for adaptive microwave front ends. Part of the ongoing research is the field of all-oxide devices, where epitaxial oxide conductors are used instead of polycrystalline metal electrodes, leading to epitaxial ferroelectric layers and resulting in high device performance. In particular, they allow engineering the acoustic properties separated from the electric ones due to the structural similarity between the dielectric and conducting oxide films. Two major results are reported in this work. First, a highly accurate model for the microwave impedance of ferroelectric varactors is derived that tracks the superposition of induced piezoelectricity and field extrusion into the substrate caused by thin electrodes. In difference to previous works, this model covers both a wide frequency and biasing range up to 12 GHz and 100 V/ [Formula: see text]. Second, the high model accuracy enables the determination of all relevant electric and mechanic properties based on a mere microwave characterization. This approach will be especially valuable when independent measurements of mechanical properties of the thin-film materials are impeded by a high integration of the devices. Though derived for all-oxide varactors, the presented model can as well be adapted for thin-film bulk acoustic wave resonators (FBARs) and varactors with conventional metal electrodes when eventual dead layers at the interface are modeled correctly.

High Voltage Electrodes for Li-Ion Batteries and Efficient Water Electrolysis: An Oxymoron?

We demonstrate that key parameters for efficient electrocatalytic oxidation of water are the energetics of the redox complexes associated with their ionization and electrochemical potentials coupled to the change of metal-oxygen band hybridization. We investigate the catalytic activity of the LiCoPO4-LiCo2P3O10 tailored compound, which is a 5 V cathode material for Li-ion batteries. The reason for the weak catalytic activity of the lithiated compound toward the oxygen evolution reaction is a large energy difference between the electronic states involved in the electrochemical reaction. A highly active catalyst is obtained by tuning the relative energetic position of the electronic levels involved in the charge transfer reaction, which in turn are governed by the lithium content. A significant lowering of the overpotential from >550 mV to ∼370 mV at 10 mA cm-2 is achieved via a decrease of the ionization potential and shifting the electrochemical potential near the electronic states of the molecule, thereby facilitating water oxidation.

BaCoO2+δ: a new highly oxygen deficient perovskite-related phase with unusual Co coordination obtained by high temperature reaction with short reaction times.

A new highly oxygen deficient metastable modification of perovskite-related BaCoO2+δ (δ ∼ 0.01-0.02) has been prepared using high temperature reactions with short heating times. This defect rich compound has at least partially square planar coordination of the Co2+ ions, a highly unusual coordination environment for Co. Low temperature neutron powder diffraction showed a G-type antiferromagnetic ordering, confirmed by SQUID magnetic measurements, which indicate a high Néel temperature of 220 K. This work shows how novel defective phases can be synthesized by exploiting short reaction times in solid state synthesis, thus offering an alternative route for new materials synthesis.

Synthesis and characterisation of fluorinated epitaxial films of BaFeO2F: tailoring magnetic anisotropy via a lowering of tetragonal distortion.

In this article, we report on the synthesis and characterisation of fluorinated epitaxial films of BaFeO2F via low-temperature fluorination of thin films of BaFeO2.5+d grown by pulsed laser deposition. Diffraction measurements show that fluoride incorporation only results in a contraction of the film perpendicular to the film surface, where clamping by the substrate is prohibitive for strong in-plane changes. The fluorinated films were found to be homogenous regarding the fluorine content over the whole film thickness, and can be considered as single crystal equivalents to the bulk phase BaFeO2F. Surprisingly, fluorination resulted in the change of the tetragonal distortion to a nearly cubic symmetry, which results in a lowering of anisotropic orientation of the magnetic moments of the antiferromagnetically ordered compound, confirmed by Mössbauer spectroscopy and magnetic studies.

In-operando photoelectron spectroscopy for batteries: Set-up using pristine thin film cathode and first results on NaxCoO2.

A model all-solid-state battery cell with a thin film NaxCoO2 cathode was assembled under ultra-high vacuum conditions and cycled inside the vacuum chamber, using a dedicated sample holder. We present in-operando x-ray photoelectron spectroscopy measurements of a NaxCoO2 cathode at different charging states. During battery operation, the change in sodium content, the change in cobalt oxidation state, and the evolution of the O1s and VB emissions could be monitored. Comparison with a conventional post-mortem analysis technique showed that the new measurement technique produces comparable results regarding the oxidation state of the transition metal, but sodium and oxygen results show differences due to cathode/electrolyte interfacial reactions for conventional analysis. By using surface layer-free samples in the presented techniques, we could circumvent such reactions and obtain reliable spectra for the pure bulk-like active cathode material.