National Institute Of Materials Physics - Romania

Synapses play a vital role in information processing, learning, and memory formation in the brain. By emulating the behavior of biological synapses, electronic synaptic devices hold the promise of enabling high-performance, energy-efficient, and scalable neuromorphic computing. Ferroelectric memristive devices integrate the characteristics of both ferroelectric and memristive materials and present a far-reaching potential as artificial synapses. Here, it is reported on a new ferroelectric device on silicon, a field-effect memristor, consisting of an epitaxial ultrathin ferroelectric Hf(0.5)Z(r0.5)O(2) film sandwiched between an epitaxial highly doped oxide semiconductor SrTiO3-delta and a top metal. Upon a low voltage of less than 2 V, the field-effect modulation in the semiconductor enables to access multiple states. The device works in a large time domain ranging from milliseconds down to tens of nanoseconds. By gradually switching the polarization by identical pulses, the ferroelectric diode devices can dynamically adjust the synaptic strength to mimic short- and long-term memory plasticity. Ionic contributions due to redox processes in the oxide semiconductor beneficially influence the device operation and retention.

A novel high-entropy perovskite powder with the composition Bi0.2K0.2Ba0.2Sr0.2Ca0.2TiO3 was successfully synthesized using a modified Pechini method. The precursor powder underwent characterization through Fourier Transform Infrared Spectroscopy and thermal analysis. The resultant Bi0.2K0.2Ba0.2Sr0.2Ca0.2TiO3 powder, obtained post-calcination at 900 C-degrees, was further examined using a variety of techniques including X-ray diffraction, Raman spectroscopy, X-ray fluorescence, scanning electron microscopy, and transmission electron microscopy. Ceramic samples were fabricated by conventional sintering at various temperatures (900, 950, and 1000 C-degrees). The structure, microstructure, and dielectric properties of these ceramics were subsequently analyzed and discussed. The ceramics exhibited a two-phase composition comprising cubic and tetragonal perovskites. The grain size was observed to increase from 35 to 50 nm, contingent on the sintering temperature. All ceramic samples demonstrated relaxor behavior with a dielectric maximum that became more flattened and shifted towards lower temperatures as the grain size decreased.

Fine-tuning of grain sizes can significantly influence the interaction between different dielectric phenomena, allowing the development of materials with tailored dielectric resistivity. By virtue of various synthesis mechanisms, a pathway to manipulate grain sizes and, consequently, tune the material's dielectric response is revealed. Understanding these intricate relationships between granulation and dielectric properties can pave the way for designing and optimizing materials for specific applications where tailored dielectric responses are sought. The experimental part involved the fabrication of dense BCT-BZT ceramics with different grain sizes by varying the synthesis (conventional solid-state reaction route and sol-gel) and consolidation methods. Both consolidation methods produced well-crystallized specimens, with Ba0.85Ca0.15O3Ti0.9Zr0.1 (BCTZ) perovskite as the major phase. Conventional sintering resulted in microstructured and submicron-structured BCT-BZT ceramics, with average grain sizes of 2.35 mu m for the solid-state sample and 0.91 mu m for the sol-gel synthesized ceramic. However, spark plasma sintering produced a nanocrystalline specimen with an average grain size of 67.5 nm. As the grain size decreases, there is a noticeable decrease in the maximum permittivity, a significant reduction in dielectric losses, and a shifting of the Curie temperature towards lower values.

This study focuses on the properties of the BiOi (interstitial Boron-interstitial Oxygen) and CiOi (interstitial Carbon-interstitial Oxygen) defect complexes by 5.5MeV electrons in low resistivity silicon. Two different types of diodes manufactured on p-type epitaxial and Czochralski silicon with a resistivity of about 10 Omega center dot cm were irradiated with fluence values between 1x10(15) cm(-2) and 6x10(15) cm(-2). Such diodes cannot be fully depleted and thus the accurate evaluation of defect concentrations and properties (activation energy, capture cross-section, concentration) from Thermally Stimulated Currents (TSC) experiments alone is not possible. In this study we demonstrate that by performing Thermally Stimulated Capacitance (TS-Cap) experiments in similar conditions to TSC measurements and developing theoretical models for simulating both types of BiOi signals generated in TSC and TS-Cap measurements, accurate evaluations can be performed. The changes of the position-dependent electric field, the effective space charge density N-eff profile as well as the occupation of the BiOi defect during the electric field dependent electron emission, are simulated as a function of temperature. The macroscopic properties (leakage current and..eff) extracted from current-voltage and capacitance-voltage measurements at 20 degrees C are also presented and discussed.

Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N-2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of approximate to 9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.

This work evaluates the effects of manganese (Mn) doping on the morpho-structural features, mechanical performance, and in vitro biological response of beta-tricalcium phosphate (beta-TCP) derived bioceramics for bone tissue engineering applications. Five different Mn doping levels (i.e., 0.01%, 0.05%, 0.1%, 0.5%, and 1 wt.%) were investigated, with the beta-TCP-based bioceramics being sintered at four temperatures (i.e., 1000, 1100, 1200, and 1300 degrees C). A densification improvement was induced when using Mn in excess of 0.05 wt.%; the densification remained stationary in the sintering temperature range of 1200 - 1300 degrees C. The structural analyses evidenced that all samples sintered at 1000 and 1100 degrees C were composed of beta-TCP as major phase and hydroxyapatite (HA) as a minor constituent (similar to 4-6 wt.%). At the higher temperatures (1200 and 1300 degrees C), the formation of alpha-TCP was signalled at the expense of both beta-TCP and HA. The Mn doping was evidenced by lattice parameters changes. The evolution of the phase weights is linked to a complex inter-play between the capacity of the compounds to incorporate Mn and the thermal decomposition kinetics. The Mn doping induced a reduction in the mechanical performance (in terms of compressive strength, Vickers hardness and elastic modulus) of the beta-TCP-based ceramics. The metabolic activity and viability of osteoblastic cells (MC3T3-E1) for the ceramics were studied in both powder and compacted pellet form. Ceramics with Mn doping levels lower than 0.1 wt.% yielded a more favorable microenvironment for the osteoblast cells with respect to the undoped beta-TCP. No cytotoxic effects were recorded up to 21 days. The Mn-doped beta-TCPs showed a significant increase (p < 0.01) in alkaline phosphatase activity with respect to pure beta-TCP.

Probing of the free surface ferroelectric properties of thin polar films can be achieved either by estimating the band bending variance under the top-most layer or by studying the extent of the extrinsic charge accumulated outside the surface. Photoemitted or incoming low-energy electrons can be used to characterize locally both properties in a spectromicroscopic approach. Thin ferroelectric lead zirco-titanate (PZT) is investigated by combining low energy/mirror electron microscopy (LEEM/MEM) with photoemission electron microscopy (PEEM) and high-resolution photoelectron spectroscopy (XPS). Significant extrinsic negative compensation charge is proven to accumulate on the surface of the outward polarized thin film, indicated by high MEM-LEEM transition values, up to 15.3 eV, and is correlated with the surface electrostatic potential, which can be partially screened either by electrons interacting with the sample or by soft X-rays through the ejection of secondary electrons and generation of positive charge under the surface. A radiation-induced surface charge compensation effect is observed. The study indicates that air-exposed high quality ferroelectric thin films show large negative surface potentials, determined locally on the surface, which are nevertheless sensitive to beam damage and molecular desorption. These values represent a confirmation of previously estimated surface potential energy values determined from the LEED data on clean surfaces.

Two new families of zinc/cobalt/aluminum-based pigments, with a unique composition, were obtained through the polyol method. The hydrolysis process of a mixture of Co(CH3COO)(2), Zn(acac)(2) and Al(acac)(3) (acac(-) = acetylacetonate ion) in 1,4-butanediol afforded dark blue gels (wPZn(x)Co(1-x)Al), in the presence of a supplementary amount of water, and light green powders (PZnxCo1-xAl), respectively, for the water-free procedure (x = 0, 0.2, 0.4). The calcination of the precursors yielded dark green (wZn(x)Co(1-x)Al) and blue (ZnxCo1-xAl) products. XRD measurements and Rietveld refinement indicate the co-existence of three spinel phases, in different proportions: ZnxCo1-xAl2O4, Co3O4 and the defect spinel, ?-Al2.67O4. The Raman scattering and XPS spectra are in agreement with the compositions of the samples. The morphology of wZn(x)Co(1-x)Al consists of large and irregular spherical particle aggregates (ca. 5-100 mm). Smaller agglomerates (ca. 1-5 mm) with a unique silkworm cocoon-like hierarchical morphology composed of cobalt aluminate cores covered with flake-like alumina shells are formed for ZnxCo1-xAl. TEM and HR-TEM analyses revealed the formation of crystalline, polyhedral particles of 7-43 nm sizes for wZn(x)Co(1-x)Al, while for ZnxCo1-xAl, a duplex-type morphology, with small (7-13 nm) and larger (30-40 nm) particles, was found. BET assessment showed that both series of oxides are mesoporous materials, with different pore structures, with the water-free samples exhibiting the largest surface areas due, most likely, to the high percent of aluminum oxide. A chemical mechanism is proposed to highlight the role of the water amount and the nature of the starting compounds in the hydrolysis reaction products and, further, in the morpho-structural features and composition of the resulting spinel oxides. The CIE L*a*b* and C* colorimetric parameters indicate that the pigments are bright, with a moderate degree of luminosity, presenting an outstanding high blueness.

Dense fine-grained Ba0.6Sr0.4TiO3 ceramics with submicronic grains sizes (GS) have been prepared using nanopowders synthesized via sol-gel route and consolidated by Spark Plasma Sintering (SPS). By changing SPS parameters, the GS was reduced from 214 nm to 74 nm. Diffuse ferroelectric-paraelectric phase transitions and low values of dielectric permittivity (<1000) at the Curie temperature (T-C similar to 280 K) were revealed by Impedance Spectroscopy in all sintered ceramics. The GS reduction from submicron to nanoscale range reflects in a gradually diminishment of dielectric constant, tunability, polarisation and storage energy properties. Raman spectroscopy investigations pointed out the presence of polar nanoclusters above the T-C. The short-range polar order is affected by the GS decrease, but becomes more thermally stable. The observed properties of Ba0.6Sr0.4TiO3 nanostructured ceramics are interpreted by considering the interplay between the GS reduction, the role of low-permittivity grain boundaries and the diffuse character of the ferroelectric-to-paraelectric transformation.

Dense fine-grained Ba0.6Sr0.4TiO3 ceramics with submicronic grains sizes (GS) have been prepared using nanopowders synthesized via sol-gel route and consolidated by Spark Plasma Sintering (SPS). By changing SPS parameters, the GS was reduced from 214 nm to 74 nm. Diffuse ferroelectric-paraelectric phase transitions and low values of dielectric permittivity (<1000) at the Curie temperature (T-C similar to 280 K) were revealed by Impedance Spectroscopy in all sintered ceramics. The GS reduction from submicron to nanoscale range reflects in a gradually diminishment of dielectric constant, tunability, polarisation and storage energy properties. Raman spectroscopy investigations pointed out the presence of polar nanoclusters above the T-C. The short-range polar order is affected by the GS decrease, but becomes more thermally stable. The observed properties of Ba0.6Sr0.4TiO3 nanostructured ceramics are interpreted by considering the interplay between the GS reduction, the role of low-permittivity grain boundaries and the diffuse character of the ferroelectric-to-paraelectric transformation.