Effect of Domain Structure and Dielectric Interlayer on Switching Speed of Ferroelectric Hf0.5Zr0.5O2 Film.

The nanosecond speed of information writing and reading is recognized as one of the main advantages of next-generation non-volatile ferroelectric memory based on hafnium oxide thin films. However, the kinetics of polarization switching in this material have a complex nature, and despite the high speed of internal switching, the real speed can deteriorate significantly due to various external reasons. In this work, we reveal that the domain structure and the dielectric layer formed at the electrode interface contribute significantly to the polarization switching speed of 10 nm thick Hf0.5Zr0.5O2 (HZO) film. The mechanism of speed degradation is related to the generation of charged defects in the film which accompany the formation of the interfacial dielectric layer during oxidization of the electrode. Such defects are pinning centers that prevent domain propagation upon polarization switching. To clarify this issue, we fabricate two types of similar W/HZO/TiN capacitor structures, differing only in the thickness of the electrode interlayer, and compare their ferroelectric (including local ferroelectric), dielectric, structural (including microstructural), chemical, and morphological properties, which are comprehensively investigated using several advanced techniques, in particular, hard X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, and electron beam induced current technique.

Wake-Up Free Ultrathin Ferroelectric Hf0.5Zr0.5O2 Films.

The development of the new generation of non-volatile high-density ferroelectric memory requires the utilization of ultrathin ferroelectric films. The most promising candidates are polycrystalline-doped HfO2 films because of their perfect compatibility with silicon technology and excellent ferroelectric properties. However, the remanent polarization of HfO2 films is known to degrade when their thickness is reduced to a few nanometers. One of the reasons for this phenomenon is the wake-up effect, which is more pronounced in the thinner the film. For the ultrathin HfO2 films, it can be so long-lasting that degradation occurs even before the wake-up procedure is completed. In this work, an approach to suppress the wake-up in ultrathin Hf0.5Zr0.5O2 films is elucidated. By engineering internal built-in fields in an as-prepared structure, a stable ferroelectricity without a wake-up effect is induced in 4.5 nm thick Hf0.5Zr0.5O2 film. By analysis of the functional characteristics of ferroelectric structures with a different pattern of internal built-in fields and their comparison with the results of in situ piezoresponse force microscopy and synchrotron X-ray micro-diffraction, the important role of built-in fields in ferroelectricity of ultrathin Hf0.5Zr0.5O2 films as well as the origin of stable ferroelectric properties is revealed.

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.

Nanoscale Doping and Its Impact on the Ferroelectric and Piezoelectric Properties of Hf0.5Zr0.5O2.

Ferroelectric hafnium oxide thin films-the most promising materials in microelectronics' non-volatile memory-exhibit both unconventional ferroelectricity and unconventional piezoelectricity. Their exact origin remains controversial, and the relationship between ferroelectric and piezoelectric properties remains unclear. We introduce a new method to investigate this issue, which consists in a local controlled modification of the ferroelectric and piezoelectric properties within a single Hf0.5Zr0.5O2 capacitor device through local doping and a further comparative nanoscopic analysis of the modified regions. By comparing the ferroelectric properties of Ga-doped Hf0.5Zr0.5O2 thin films with the results of piezoresponse force microscopy and their simulation, as well as with the results of in situ synchrotron X-ray microdiffractometry, we demonstrate that, depending on the doping concentration, ferroelectric Hf0.5Zr0.5O2 has either a negative or a positive longitudinal piezoelectric coefficient, and its maximal value is -0.3 pm/V. This is several hundreds or thousands of times less than those of classical ferroelectrics. These changes in piezoelectric properties are accompanied by either improved or decreased remnant polarization, as well as partial or complete domain switching. We conclude that various ferroelectric and piezoelectric properties, and the relationships between them, can be designed for Hf0.5Zr0.5O2 via oxygen vacancies and mechanical-strain engineering, e.g., by doping ferroelectric films.

Nanoparticle-Doped Hybrid Polyelectrolyte Microcapsules with Controlled Photoluminescence for Potential Bioimaging Applications.

Fluorescent imaging is widely used in the diagnosis and tracking of the distribution, interaction, and transformation processes at molecular, cellular, and tissue levels. To be detectable, delivery systems should exhibit a strong and bright fluorescence. Quantum dots (QDs) are highly photostable fluorescent semiconductor nanocrystals with wide absorption spectra and narrow, size-tunable emission spectra, which make them suitable fluorescent nanolabels to be embedded into microparticles used as bioimaging and theranostic agents. The layer-by-layer deposition approach allows the entrapping of QDs, resulting in bright fluorescent microcapsules with tunable surface charge, size, rigidity, and functional properties. Here, we report on the engineering and validation of the structural and photoluminescent characteristics of nanoparticle-doped hybrid microcapsules assembled by the deposition of alternating oppositely charged polyelectrolytes, water-soluble PEGylated core/shell QDs with a cadmium selenide core and a zinc sulfide shell (CdSe/ZnS), and carboxylated magnetic nanoparticles (MNPs) onto calcium carbonate microtemplates. The results demonstrate the efficiency of the layer-by-layer approach to designing QD-, MNP-doped microcapsules with controlled photoluminescence properties, and pave the way for the further development of next-generation bioimaging agents based on hybrid materials for continuous fluorescence imaging.

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.

Controlling Charge Transfer from Quantum Dots to Polyelectrolyte Layers Extends Prospective Applications of Magneto-Optical Microcapsules.

The layer-by-layer (LbL) deposition approach allows combined incorporation of fluorescent, magnetic, and plasmonic nanoparticles into the shell of polyelectrolyte microcapsules to obtain stimulus-responsive systems whose imaging and drug release functions can be triggered by external stimuli. The combined use of fluorescent quantum dots (QDs) and magnetic nanoparticles (MNPs) yields magnetic-field-driven imaging tools that can be tracked and imaged even deep in tissue when the appropriate type of QDs and wavelength of their excitation are used. QDs are excellent photonic labels for microcapsule encoding due to their close-to-unity photoluminescence (PL) quantum yields, narrow PL emission bands, and tremendous one- and two-photon extinction coefficients. However, the presence of MNPs and electrically charged polyelectrolyte molecules used for the LbL fabrication of magneto-optical microcapsules provokes alterations of the QD optical properties because of the photoinduced charge and energy transfer resulting in QD photodarkening or photobrightening. These lead to variation of the microcapsule PL signal under illumination, which hampers their tracking and quantitative analysis in cells and tissues. Here, we have studied the effects of the structure and spatial arrangement of the nanoparticles within the microcapsule polyelectrolyte shell, the total shell thickness, and the shell surface charge on their PL properties under continuous illumination. The roles of the charge transfer and its main driving forces in the stability of the microcapsules PL signal have been established, and the design of the microcapsules dually encoded with QDs and MNPs providing the strongest and most stable PL has been determined. Controlling the energy transfer from the QDs and MNPs and the charge transfer from QDs to polyelectrolyte layers in the engineering of magneto-optical microcapsules with a bright and stable PL signal extends their applications to long-lasting quantitative fluorescence imaging.

Next-Generation Theranostic Agents Based on Polyelectrolyte Microcapsules Encoded with Semiconductor Nanocrystals: Development and Functional Characterization.

Fabrication of polyelectrolyte microcapsules and their use as carriers of drugs, fluorescent labels, and metal nanoparticles is a promising approach to designing theranostic agents. Semiconductor quantum dots (QDs) are characterized by extremely high brightness and photostability that make them attractive fluorescent labels for visualization of intracellular penetration and delivery of such microcapsules. Here, we describe an approach to design, fabricate, and characterize physico-chemical and functional properties of polyelectrolyte microcapsules encoded with water-solubilized and stabilized with three-functional polyethylene glycol derivatives core/shell QDs. Developed microcapsules were characterized by dynamic light scattering, electrophoretic mobility, scanning electronic microscopy, and fluorescence and confocal microscopy approaches, providing exact data on their size distribution, surface charge, morphological, and optical characteristics. The fluorescence lifetimes of the QD-encoded microcapsules were also measured, and their dependence on time after preparation of the microcapsules was evaluated. The optimal content of QDs used for encoding procedure providing the optimal fluorescence properties of the encoded microcapsules was determined. Finally, the intracellular microcapsule uptake by murine macrophages was demonstrated, thus confirming the possibility of efficient use of developed system for live cell imaging and visualization of microcapsule transportation and delivery within the living cells.

Impedance spectroscopy of single bacterial nanofilament reveals water-mediated charge transfer.

For decades respiratory chain and photosystems were the main firing field of the studies devoted to mechanisms of electron transfer in proteins. The concept of conjugated lateral electron and transverse proton transport during cellular respiration and photosynthesis, which was formulated in the beginning of 1960-s, has been confirmed by thousands of experiments. However, charge transfer in recently discovered bacterial nanofilaments produced by various electrogenic bacteria is regarded currently outside of electron and proton conjugation concept. Here we report the new study of charge transfer within nanofilaments produced by Shewanella oneidensis MR-1 conducted in atmosphere of different relative humidity (RH). We utilize impedance spectroscopy and DC (direct current) transport measurements to find out the peculiarities of conductivity and Raman spectroscopy to analyze the nanofilaments' composition. Data analysis demonstrates that apparent conductivity of nanofilaments has crucial sensitivity to humidity and contains several components including one with unusual behavior which we assign to electron transport. We demonstrate that in the case of Shewanella oneidensis MR-1 charge transfer within these objects is strongly mediated by water. Basing on current data analysis of conductivity we conclude that the studied filaments of Shewanella oneidensis MR-1 are capable of hybrid (conjugated) electron and ion conductivity.

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.