Retention Improvement of HZO-Based Ferroelectric Capacitors with TiO2 Insets.

The influence of the bottom TiO2 interfacial layer grown by atomic layer deposition on the ferroelectric properties of the TiN/Hf0.5Zr0.5O2/TiN capacitors is systematically investigated. We show that the integration of the TiO2 layer leads to an increase in the polar orthorhombic phase content in the Hf0.5Zr0.5O2 film. In addition, the crystalline structure of the Hf0.5Zr0.5O2 film is highly dependent on the thickness of the TiO2 inset, with monoclinic phase stabilization after the increase of TiO2 thickness. Special attention in this work is given to the key reliability parameters-retention and endurance. We demonstrate that the integration of the TiO2 inset induces valuable retention improvement. Using a novel approach to the depolarization measurements, we show that the depolarization contribution to the retention loss is insignificant, which leaves the imprint effect as the root of the retention loss in TiN/TiO2/Hf0.5Zr0.5O2/TiN devices. We believe that the integration of the insulator interfacial layer suppresses the scavenging effect from the bottom TiN electrode, leading to a decrease in the oxygen vacancy content in the Hf0.5Zr0.5O2 film, which is the main reason for imprint mitigation. At the same time, although the observed retention improvement is very promising for the upcoming technological integration, the field cycling testing revealed the endurance limitations linked to the phase transitions in the TiO2 layer and the rise of the effective electric field applied to the Hf0.5Zr0.5O2 film.

Field-Effect Transistor Based on 2D Microcrystalline MoS2 Film Grown by Sulfurization of Atomically Layer Deposited MoO3.

Atomically thin molybdenum disulfide (MoS2) is a promising channel material for next-generation thin-body field-effect transistors (FETs), which makes the development of methods allowing for its controllable synthesis over a large area an essential task. Currently, one of the cost-effective ways of its synthesis is the sulfurization of preliminary grown oxide- or metallic film. However, despite apparent progress in this field, the electronic quality of the obtained MoS2 is inferior to that of exfoliated samples, making the detailed investigation of the sulfurized films' properties of great interest. In this work, we synthesized continuous MoS2 films with a thickness of ≈2.2 nm via the sulfurization of an atomic-layer-deposited MoO3 layer. X-ray photoelectron spectroscopy, transmission electron microscopy, and Raman spectroscopy indicated the appropriate chemical composition and microcrystalline structure of the obtained MoS2 films. The semiconductor quality of the synthesized films was confirmed by the fabrication of a field-effect transistor (FET) with an Ion/Ioff ratio of ≈40, which was limited primarily by the high contact resistance. The Schottky barrier height at the Au/MoS2 interface was found to be ≈1.2 eV indicating the necessity of careful contact engineering. Due to its simplicity and cost-effectiveness, such a technique of MoS2 synthesis still appears to be highly attractive for its applications in next-generation microelectronics. Therefore, further research of the electronic properties of films obtained via this technique is required.

On the Reliability of HZO-Based Ferroelectric Capacitors: The Cases of Ru and TiN Electrodes.

Despite the great potential of Hf0.5Zr0.5O2 (HZO) ferroelectrics, reliability issues, such as wake-up, fatigue, endurance limitations, imprint and retention loss, impede the implementation of HZO to nonvolatile memory devices. Herein, a study of the reliability properties in HZO-based stacks with the conventional TiN top electrode and Ru electrode, which is considered a promising alternative to TiN, is performed. An attempt to distinguish the mechanisms underlying the wake-up, fatigue and retention loss in both kinds of stacks is undertaken. Overall, both stacks show pronounced wake-up and retention loss. Moreover, the fatigue and retention loss were found to be worsened by Ru implementation. The huge fatigue was suggested to be because Ru does not protect HZO against oxygen vacancies generation during prolonged cycling. The vacancies generated in the presence of Ru are most likely deeper traps, as compared to the traps formed at the interface with the TiN electrode. Implementing the new procedure, which can separate the depolarization-caused retention loss from the imprint-caused one, reveal a rise in the depolarization contribution with Ru implementation, accompanied by the maintenance of similarly high imprint, as in the case with the TiN electrode. Results show that the mechanisms behind the reliability issues in HZO-based capacitors are very electrode dependent and simple approaches to replacing the TiN electrode with the one providing, for example, just higher remnant polarization or lower leakages, become irrelevant on closer examination.

Thickness-Dependent Structural and Electrical Properties of WS2 Nanosheets Obtained via the ALD-Grown WO3 Sulfurization Technique as a Channel Material for Field-Effect Transistors.

Ultrathin WS2 films are promising functional materials for electronic and optoelectronic devices. Therefore, their synthesis over a large area, allowing control over their thickness and structure, is an essential task. In this work, we investigated the influence of atomic layer deposition (ALD)-grown WO3 seed-film thickness on the structural and electrical properties of WS2 nanosheets obtained via a sulfurization technique. Transmission electron microscopy indicated that the thinnest (1.9 nm) film contains rather big (up to 50 nm) WS2 grains in the amorphous matrix. The signs of incomplete sulfurization, namely, oxysulfide phase presence, were found by X-ray photoemission spectroscopy analysis. The increase in the seed-film thickness of up to 4.7 nm resulted in a visible grain size decrease down to 15-20 nm, which was accompanied by defect suppression. The observed structural evolution affected the film resistivity, which was found to decrease from ∼106 to 103 (µΩ·cm) within the investigated thickness range. These results show that the thickness of the ALD-grown seed layer may strongly affect the resultant WS2 structure and properties. Most valuably, it was shown that the growth of the thinnest WS2 film (3-4 monolayers) is most challenging due to the amorphous intergrain phase formation, and further investigations focused on preventing the intergrain phase formation should be conducted.

Impact of the Atomic Layer-Deposited Ru Electrode Surface Morphology on Resistive Switching Properties of TaOx-Based Memory Structures.

Resistive switching (RS) device behavior is highly dependent on both insulator and electrode material properties. In particular, the bottom electrode (BE) surface morphology can strongly affect RS characteristics. In this work, Ru films with different thicknesses grown on a TiN layer by radical-enhanced atomic layer deposition (REALD) are used as an inert BE in TaOx-based RS structures. The REALD Ru surface roughness is found to increase by more than 1 order of magnitude with the increase in the reaction cycle number. Simultaneously, a wide range of RS parameters, such as switching voltage, resistance both in low and high resistance states, endurance, and so forth, monotonically change. A simplified model is proposed to explain the linkage between RS properties and roughness of the Ru surface. The field distribution was simulated based on the observed surface morphologies, and the resulting conducting filament formation was anticipated based on the local field enhancement. Conductive atomic force microscopy confirmed the theoretical expectations.

The Effect of Five-Day Dry Immersion on the Nervous and Metabolic Mechanisms of the Circulatory System.

The purpose of the study was to investigate the regulatory and metabolic changes in the circulatory system when simulating microgravity conditions in a five-day dry immersion. These changes reflect the adaptation processes characteristic for the initial stages of a space flight or a short-duration space flight. Studies were conducted with 13 healthy male volunteers aged 21 to 29 years. The assessment of regulatory and metabolic processes in the circulatory system was based on the heart rate variability (HRV) and urine proteomic profile analysis. It was found that the restructuring of hemodynamics during 5 days hypogravity begins with the inclusion of the nervous circuit of regulation, and for manifestations at the body fluids protein composition level and activation of the metabolic regulation, these periods are apparently insufficient. Perhaps this is due to the fact that the metabolic regulation, being evolutionarily ancient and genetically determined, is more stable and requires more time for its pronounced activation when stimulated by extreme life conditions.

Urine proteome changes associated with autonomic regulation of heart rate in cosmonauts.

BACKGROUND: The strategy of adaptation of the human body in microgravity is largely associated with the plasticity of cardiovascular system regulatory mechanisms. During long-term space flights the changes in the stroke volume of the heart are observed, the heart rate decreases, the phase structure of cardiac cycle is readjusted The purpose of this work was to clarify urine proteome changes associated with the initial condition of the heart rate autonomic regulation mechanisms in cosmonauts who have participated in long space missions. Urine proteome of each cosmonaut was analyzed before and after space flight, depending on the initial parameters characterizing the regulatory mechanisms of the cardiovascular system. RESULTS: The proteins cadherin-13, mucin-1, alpha-1 of collagen subunit type VI (COL6A1), hemisentin-1, semenogelin-2, SH3 domain-binding protein, transthyretin and serine proteases inhibitors realize a homeostatic role in individuals with different initial type of the cardiovascular system regulation. The role of significantly changed urine proteins in the cardiovascular homeostasis maintenance is associated with complex processes of atherogenesis, neoangiogenesis, activation of calcium channels, changes in cell adhesion and transmembrane properties, changes in extracellular matrix, participation in protection from oxidative stress and leveling the effects of hypoxia. Therefore, the concentrations of these proteins significantly differ between groups with dominant parasympathetic and sympathetic influences. CONCLUSION: The space flight induced urine proteome changes are significantly different in the groups identified by heart rate autonomic regulation peculiarities before space flight. All these proteins regulate the associated biological processes which affect the stiffness of the vascular wall, blood pressure level, the severity of atherosclerotic changes, the rate and degree of age-related involution of elastin and fibulin, age-related increase in collagen stiffness, genetically determined features of elastin fibers. The increased vascular rigidity (including the aorta) and of myocardium may be regarded as a universal response to various extreme factors. Significant differences in the semi-quantitative analysis of signal proteins between groups with different types of autonomic regulation are explained by a common goal: to ensure optimal adaptation regardless of age and of the genetically determined type of responses to the extreme environmental factors effects.

Ferroelectricity in Hf0.5Zr0.5O2 Thin Films: A Microscopic Study of the Polarization Switching Phenomenon and Field-Induced Phase Transformations.

Because of their full compatibility with the modern Si-based technology, the HfO2-based ferroelectric films have recently emerged as viable candidates for application in nonvolatile memory devices. However, despite significant efforts, the mechanism of the polarization switching in this material is still under debate. In this work, we elucidate the microscopic nature of the polarization switching process in functional Hf0.5Zr0.5O2-based ferroelectric capacitors during its operation. In particular, the static domain structure and its switching dynamics following the application of the external electric field have been monitored with the advanced piezoresponse force microscopy (PFM) technique providing a nm resolution. Separate domains with strong built-in electric field have been found. Piezoresponse mapping of pristine Hf0.5Zr0.5O2 films revealed the mixture of polar phase grains and regions with low piezoresponse as well as the continuum of polarization orientations in the grains of polar orthorhombic phase. PFM data combined with the structural analysis of pristine versus trained film by plan-view transmission electron microscopy both speak in support of a monoclinic-to-orthorhombic phase transition in ferroelectric Hf0.5Zr0.5O2 layer during the wake-up process under an electrical stress.

Improved Ferroelectric Switching Endurance of La-Doped Hf0.5Zr0.5O2 Thin Films.

Hf0.5Zr0.5O2 thin films are one of the most appealing HfO2-based ferroelectric thin films, which have been researched extensively for their applications in ferroelectric memory devices. In this work, a 1 mol % La-doped Hf0.5Zr0.5O2 thin film was grown by plasma-assisted atomic layer deposition and annealed at temperatures of 450 and 500 °C to crystallize the film into the desired orthorhombic phase. Despite the use of a lower temperature than that used in previous reports, the film showed highly promising ferroelectric properties-a remnant polarization of ∼30 µC/cm2 and switching cycle endurance up to 4 × 1010. The performance was much better than that of undoped Hf0.5Zr0.5O2 thin films, demonstrating the positive influence of La doping. Such improvements were mainly attributed to the decreased coercive field (by ∼30% compared to the undoped film), which allowed for the use of a lower applied field to drive the cycling tests while maintaining a high polarization value. La doping also decreased the leakage current by ∼3 orders of magnitude compared to the undoped film, which also contributed to the strongly improved endurance. Nonetheless, the La-doped film required a larger number of wake-up cycles (∼106 cycles) to reach a saturated remnant polarization value. This behavior might be explained by the increased generation of oxygen vacancies and slower migration of these vacancies from the interface to the bulk region. However, the maximum number of wake-up cycles was less than 0.01% of the total possible cycles, and therefore, initializing the film to the maximum performance state would not be a serious burden.

Effect of Polarization Reversal in Ferroelectric TiN/Hf0.5Zr0.5O2/TiN Devices on Electronic Conditions at Interfaces Studied in Operando by Hard X-ray Photoemission Spectroscopy.

Because of their compatibility with modern Si-based technology, HfO2-based ferroelectric films have recently attracted attention as strong candidates for applications in memory devices, in particular, ferroelectric field-effect transistors or ferroelectric tunnel junctions. A key property defining the functionality of these devices is the polarization dependent change of the electronic band alignment at the metal/ferroelectric interface. Here, we report on the effect of polarization reversal in functional ferroelectric TiN/Hf0.5Zr0.5O2/TiN capacitors on the potential distribution across the stack and the electronic band line-up at the interfaces studied in operando by hard X-ray photoemission spectroscopy. By tracking changes in the position of Hf0.5Zr0.5O2 core-level lines with respect to those of the TiN electrode in both short- and open-circuit configurations following in situ polarization reversal, we derive the conduction band offset to be 0.7 (1.0) eV at the top and 1.7 (1.0) eV at the bottom interfaces for polarization, pointing up (down), respectively. Energy dispersive X-ray spectroscopy profiling of the sample cross-section in combination with the laboratory X-ray photoelectron spectroscopy reveal the presence of a TiOx/TiON layer at  both interfaces. The observed asymmetry in the band line-up changes in the TiN/Hf0.5Zr0.5O2/TiN memory stack is explained by different origin of these oxidized layers and effective pinning of polarization at the top interface. The described methodology and first experimental results are useful for the optimization of HfO2-based ferroelectric memory devices under development.

Ultrathin Hf0.5Zr0.5O2 Ferroelectric Films on Si.

Because of their immense scalability and manufacturability potential, the HfO2-based ferroelectric films attract significant attention as strong candidates for application in ferroelectric memories and related electronic devices. Here, we report the ferroelectric behavior of ultrathin Hf0.5Zr0.5O2 films, with the thickness of just 2.5 nm, which makes them suitable for use in ferroelectric tunnel junctions, thereby further expanding the area of their practical application. Transmission electron microscopy and electron diffraction analysis of the films grown on highly doped Si substrates confirms formation of the fully crystalline non-centrosymmetric orthorhombic phase responsible for ferroelectricity in Hf0.5Zr0.5O2. Piezoresponse force microscopy and pulsed switching testing performed on the deposited top TiN electrodes provide further evidence of the ferroelectric behavior of the Hf0.5Zr0.5O2 films. The electronic band lineup at the top TiN/Hf0.5Zr0.5O2 interface and band bending at the adjacent n(+)-Si bottom layer attributed to the polarization charges in Hf0.5Zr0.5O2 have been determined using in situ X-ray photoelectron spectroscopy analysis. The obtained results represent a significant step toward the experimental implementation of Si-based ferroelectric tunnel junctions.